Catalytic reduction of nitrogen oxides

ABSTRACT

This invention relates to a method for catalytically reducing one or more nitrogen oxides from a gaseous stream containing one or more nitrogen oxides and one or more sulfur oxides which comprises contacting said gaseous stream and ammonia with a microporous non-zeolitic molecular sieve composition at effective reduction conditions, wherein said microporous non-zeolitic molecular sieve composition is (i) optionally acid treated with an inorganic or organic acid, (ii) hydrogen-forming cation exchanged and (iii) optionally metal cation exchanged, prior to said contacting in said method.

BRIEF SUMMARY OF THE INVENTION Technical Field

This invention relates to the catalytic reduction of nitrogen oxides. Inparticular, this invention relates to the catalytic reduction of noxiousnitrogen oxides present in waste gaseous streams by utilizing speciallytreated microporous non-zeolitic molecular sieve compositions ascatalysts. This invention provides for the effective elimination ofnoxious nitrogen oxides as a source of pollution from fossil-fuel-firedpower generation plants and other industrial plant off-gas streams.

BACKGROUND OF THE INVENTION

It is generally recognized that atmospheric pollution is a seriousproblem existing in the world today. It is also recognized that certainnitrogen oxides contribute significantly to this problem.

There are a least six stable oxides of nitrogen but only nitric oxide(NO) and nitrogen dioxide (NO₂) are troublesome from a pollutionstandpoint. In common with other major air pollutants, these noxiousnitrogen oxides arise chiefly from the production of energy, morespecifically by the fixation of atmospheric nitrogen in high temperatureregions of furnaces and internal combustion engines. Another source ofthese noxious nitrogen oxides are inorganic and organic nitrationreactions in chemical process industries. Transportation, industry andelectricity generation all contribute to the problem.

Oxides of nitrogen play a dual role in air pollution, first as apollutant in their own right and second as the initiator of complexphotochemical reactions with hydrocarbons. While photochemical smog isthe most visible and immediately serious consequence of pollution bythese noxious nitrogen oxides, e.g., adverse effects on human health, itis recognized that the presence of these noxious nitrogen oxides in theatmosphere will adversely affect the environment even though nophotochemical smog has ever been detected in the particular environment.It is most important, therefore, that noxious nitrogen oxides be removedfrom exhaust gases emitted from polluting sources such as power plants,nitric acid plants, automobiles and the like.

Various methods have been proposed for removing noxious nitrogen oxidesfrom gas streams and preventing the pollution of the atmosphere withthese substances.

U.S. Pat. No. 4,220,632 describes noxious nitrogen oxides in a waste gasstream such as the stack gas from a fossil-fuel fired power generationplant or other industrial plant off gas stream which are catalyticallyreduced to elemental nitrogen and/or innocuous nitrogen oxides employingammonia as a reductant in the presence of a zeolite catalyst in thehydrogen or sodium form having pore openings of about 3 to 10 Angstroms.

U.S. Pat. No. 3,895,094 discloses oxides of nitrogen which areselectively removed from air-polluting exhaust gases from nitric acidmanufacturing plants by reaction with a stoichiometric amount of ammoniain the presence of an acid resistant aluminosilicate molecular sievecomposition as catalyst.

U.K. Patent No. GB 2,039,863 describes a process for the reduction ofnitrogen oxides with ammonia, when the nitrogen oxides to be reduced arein a gas mixture containing up to 21% by volume oxygen in which the gasstream to be treated is passed over clinoptilolite predominantly in thehydrogen form, the temperature being greater than 200° C., spacevelocity being 4000 to 20,000 hr⁻¹ and the molar ratio of NH₃ tonitrogen oxides being in the range of 0.4 to 2.5.

U.S. Pat. No. 4,473,535 discloses a process for reducing nitric oxidewith ammonia in the presence of a copper exchanged mordenite catalyst ata temperature between about 300° F. and 800° F.

U.S. Pat. No. 4,046,888 relates to a method for selectively reducingnitrogen oxides contained in exhaust gases by using ammonia as areducing agent and a zeolite catalyst in which the zeolite catalyst iscontacted with ammonia in an amount excessive over the stoichiometricamount necessary for reduction of nitrogen oxides in an exhaust gas tothereby activate the zeolite catalyst and then, the amount of ammonia isreduced to a minimum amount necessary for reduction of nitrogen oxidesto effect the catalytic reduction.

DISCLOSURE OF THE INVENTION

This invention relates to a method for catalytically reducing one ormore nitrogen oxides from a gaseous stream containing one or morenitrogen oxides (NO_(x)) and one or more sulfur oxides (SO_(x)) whichcomprises contacting said gaseous stream and ammonia with a microporousnon-zeolitic molecular sieve composition at effective reductionconditions, wherein said microporous non-zeolitic molecular sievecomposition is (i) optionally acid treated with an inorganic or organicacid, (ii) hydrogen-forming cation exchanged and (iii) optionally metalcation exchanged, prior to said contacting in said method.

DETAILED DESCRIPTION

As indicated above, this invention relates to a method for catalyticallyreducing one or more nitrogen oxides from a gaseous stream containingone or more nitrogen oxides and one or more sulfur oxides whichcomprises contacting said gaseous stream and ammonia with a microporousnon zeolitic molecular sieve composition at effective reductionconditions, wherein said microporous non zeolitic molecular sievecomposition is (i) optionally acid treated with an inorganic or organicacid, (ii) hydrogen-forming cation exchanged and (iii) optionally metalcation exchanged, prior to said contacting in said method.

Copending U.S. patent application Ser. No. 178,978, filed on an evendate herewith and commonly assigned, relates to a method forcatalytically reducing one or more nitrogen oxides from a gaseous streamcontaining one or more nitrogen oxides and one or more sulfur oxideswhich comprises contacting said gaseous stream and ammonia with amulti-dimensional, microporous molecular sieve composition having a SiO₂/Al₂ O₃ molar ratio of greater than about 6.5 at effective reductionconditions, wherein said multi-dimensional, microporous molecular sievecomposition is (i) acid treated with an inorganic or organic acid, (ii)hydorgen forming cation exchanged and (iii) metal cation exchanged,prior to said contacting in said method.

Copending U.S. patent application Ser. No. 178,578, filed on an evendate herewith and commonly assigned, relates to a method forcatalytically reducing one or more nitrogen oxides from a gaseous streamcontaining one or more nitrogen oxides and optionally one or more sulfuroxides which comprises contacting said gaseous stream and ammonia with amicroporous molecular sieve composition at effective reductionconditions in which the amount of ammonia in said method is excessiveover the stoichiometric amount necessary for catalytically reducing oneor more nitrogen oxides from said gaseous stream, wherein saidmicroporous molecular sieve composition is (i) optionally acid treatedwith an inorganic or organic acid, (ii) hydrogen forming cationexchanged and (iii) optionally metal cation exchanged, prior to saidcontacting in said method, and wherein at least a portion of excessiveammonia in said method is oxidized without substantial adverse effect oncatalytically reducing one or more nitrogen oxides from said gaseousstream.

The basic chemical reactions effected by the method of this inventionare believed to be the catalyzed reduction of a nitrogen oxide to freenitrogen with ammonia at reductive reaction temperatures and pressures,and are represented by the following equations:

    4NO+4NH.sub.3 +O.sub.2 →4N.sub.2 +6H.sub.2 O

    6NO+4NH.sub.3 →5N.sub.2 +6H.sub.2 O

    6NO.sub.2 +8NH.sub.3 →7N.sub.2 +12H.sub.2 O

    2NO.sub.2 +2NH.sub.3 →NH.sub.4 NO.sub.3 +N.sub.2 +H.sub.2 O

    NH.sub.4 NO.sub.3 →N.sub.2 O+2H.sub.2 O

    3N.sub.2 O+2NH.sub.3 →4N.sub.2 +3H.sub.2 O

The exact reactions involved in the method of this invention aredependent on the composition of the gaseous stream and the catalytic bedoperating conditions.

The source of the gaseous stream containing the nitrogen oxides, to bereductively removed by the method of this invention, will typically bean industrial flue gas, such as the flue gas from a power generatingfacility. These flue gases generally comprise, in varying relativeamounts, a mixture of oxygen, water vapor, carbon dioxide, sulfuroxides, nitrogen oxides and nitrogen.

The amount of ammonia employed should be sufficient to effect completereduction of the nitrogen oxides to elemental nitrogen and/or nitrousoxide. The amount of ammonia required will fall in a range betweenslightly less than stoichiometric and slightly more than stoichiometricbased on complete reduction to nitrogen. If no or very little oxygen ispresent in the gaseous stream, the small amounts of reducing gas (CO andH₂) present therein may reduce a part of the NO_(x) so that less than astoichiometric quantity of ammonia would be sufficient. If all or amajor proportion of NO_(x) is NO₂, the ammonia may reduce this to N₂ Owhereby less than a stoichiometric quantity based on complete reductionto nitrogen would be required. Also, particularly at highertemperatures, the microporous non-zeolitic molecular sieve catalystcomposition can reduce the NO₂ to NO so that less ammonia will berequired. On the other hand, particularly at higher temperatures,competing reactions may make it necessary to employ a little moreammonia. The exact amount of ammonia required is determined by theamount of NO_(x) in the process effluent. Ammonia is added to and mixedwith the gaseous stream prior to contact with the molecular sievecatalyst composition. It is preferred that the quantity of ammonia addedbe sufficient to obtain a mole ratio of ammonia to nitrogen oxide offrom about 0.75:1.00 to about 1.50:1.00.

In addition to effective catalytic reduction of nitrogen oxides inaccordance with the method of this invention, any excess ammoniautilized in the catalytic reduction reaction may be oxidized without anadverse effect on nitrogen oxide (NO_(x)) conversion rates. The basicchemical reactions are believed to be represented by the followingequations:

    4 NH.sub.3 +3 O.sub.2 →2 N.sub.2 +6 H.sub.2 O

    2 NH.sub.3 +2 O.sub.2 →N.sub.2 O+3 H.sub.2 O

The exact reactions involved are dependent on the catalytic bedoperating conditions.

The method of this invention further includes the utilization of amicroporous non-zeolitic molecular sieve composition including mixturesthereof as a catalyst. As described more fully hereinafter, themolecular sieve compositions are acid treated with an inorganic ororganic acid, hydrogen-forming cation exchanged and metal cationexchanged, prior to contacting with ammonia and the gaseous stream inthe method of this invention.

Molecular sieves of the non zeolitic variety include those having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(Q.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2              (I)

where "Q" represents at least one element present as a framework oxideunit "QO₂ ^(n) " with charge "n" where "n" may be -3, -2, -1, 0 or +1;"R" represents at least one organic templating agent present on theintracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Q_(w) Al_(x) P_(y) Si_(z))O₂ and has a value fromzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of QO₂ ^(n), AlO₂ ⁻, PO₂ ⁺, SiO₂, respectively, present asframework oxide units. "Q" is characterized as an element having a mean"T--O" distance in tetrahedral oxide structures between about 1.51Angstroms and about 2.06 Angstroms. "Q" has a cation electronegativitybetween about 125 kcal/gm atom to about 310 kcal/gm-atom and "Q" iscapable of forming stable Q--O--P, Q--O--Al or Q--O--Q bonds incrystalline three dimensional oxide structures having a "Q--O" bondissociation energy greater than about 59 kcal/gm atom at 298° K.; andsaid mole fractions being within the limiting compositional values orpoints as follows:

w is equal to 0 to 98 mole percent;

y is equal to 1 to 99 mole percent;

x is equal to 1 to 99 mole percent; and

z is equal to 0 to 99 mole percent.

The "Q" of the "QAPSO" molecular sieves of formula (I) may be defined asrepresenting at least one element capable of forming a frameworktetrahedral oxide and may be one of the elements arsenic, beryllium,boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium,manganese, titanium, vanadium and zinc. The invention contemplatescombinations of the elements as representing Q, and to the extent suchcombinations are present in the structure of a QAPSO they may be presentin molar fractions of the Q component in the range of 1 to 99 percentthereof. It should be noted that formula (I) contemplates the nonexistance of Q and Si. In such case, the operative structure is that ofaluminophosphate or AlPO₄. Where z has a positive value, then theoperative structure is that of silicoaluminophosphate or SAPO, discussedbelow. Thus, the term QAPSO does not perforce represent that theelements Q and Si are present. When Q is a multiplicity of elements,then to the extent the elements present are as herein contemplated, theoperative structure is that of the ELAPSO's or ELAPO's or MeAPO's orMeAPSO's, as herein discussed. However, in the contemplation thatmolecular sieves of the QAPSO variety will be invented in which Q willbe another element or elements, then it is the intention to embrace thesame as a suitable molecular sieve for the practice of this invention.

Illustrations of QAPSO compositions and structures are the variousnon-zeolitic compositions and structures described hereinbelow.

NON-ZEOLITIC MOLECULAR SIEVES

The term "non zeolitic molecular sieves" or "NZMS" is defined in theinstant invention to include the "SAPO" molecular sieves of U.S. Pat.No. 4,440,871 and U.S. Ser. No. 575,745, filed Jan. 31, 1984, "ELAPSO"molecular sieves as disclosed in U.S. Ser. No. 600,312, filed Apr. 13,1984, and certain "AlPO₄ ", "MeAPO", "FeAPO", "TAPO" and "ELAPO"molecular sieves, as hereinafter described. Crystalline "AlPO₄ "aluminophosphates are disclosed in U.S. Pat. No. 4,310,440 issued Jan.12, 1982, and in U.S. Ser. No. 880,559, filed June 30, 1986; crystallinemetal aluminophosphates (MeAPOs where "Me" is at least one of Mg, Mn, Coand Zn) are disclosed in U.S. Pat. No. 4,567,029, issued Jan. 28, 1986;crystalline ferroaluminophosphates (FeAPOs) are disclosed in U.S. Pat.No. 4,554,143, issued November 19, 1985; titanium aluminophosphates(TAPOs) are disclosed in U.S. Pat. No. 4,500,651, issued Feb. 19, 1985;certain non-zeolitic molecular sieves ("ELAPO") are disclosed in EPCPatent Application Nos. 85104386.9 (Publication No. 0158976, publishedOct. 13, 1985) and 85104388.5 (Publication No. 158349, published Oct.16, 1985); and ELAPSO molecular sieves are disclosed in copending U.S.Ser. No. 600,312, filed Apr. 13, 1984 (EPC Publication No. 0159624,published Oct. 30, 1985). The aforementioned applications and patentsare incorporated herein by reference thereto. The nomenclature employedherein to refer to the members of the aforementioned NZMSs is consistentwith that employed in the aforementioned applications or patents. Aparticular member of a class is generally referred to as a "-n" specieswherein "n" is an integer, e.g., SAPO-11, MeAPO-11 and ELAPSO-31. In thefollowing discussion on NZMSs set forth hereinafter the mole fraction ofthe NZMSs are defined as compositional values which are plotted in phasediagrams in each of the identified patents, published applications orcopending applications.

ELAPSO MOLECULAR SIEVES

"ELAPSO" molecular sieves are described in copending U.S. Ser. No.600,312, filed Apr. 13, 1984, (EPC Publication No. 0159,624, publishedOct. 30, 1985, incorporated herein by reference) as crystallinemolecular sieves having three-dimensional microporous frameworkstructures of ELO₂, AlO₂, PO₂, SiO₂ oxide units and having an empiricalchemical composition on an anhydrous basis expressed by the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; "EL" represents at least one element capable offorming a three dimensional oxide framework, "EL" being characterized asan element having a mean "T--O" distance in tetrahedral oxide structuresbetween about 1.51 Angstroms and about 2.06 Angstroms, "EL" having acation electronegativity between about 125 Kcal/g-atom to about 310Kcal/gm atom and "EL" being capable of forming stable M--O--P, M--O--Alor M--O--M bonds in crystalline three dimensional oxide structureshaving a "M--O" bond dissociation energy greater than about 59kcal/g-atom at 298° K.; and "w", "x", "y" and "z" represent the molefractions of "EL", aluminum, phosphorus and silicon, respectively,present as framework oxides, said mole fractions being within thelimiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point  x             y         (z + w)                                        ______________________________________                                        A      0.60          0.39- (0.01)p                                                                           0.01(p + 1)                                    B      0.39- (0.01p) 0.60      0.01(p + 1)                                    C      0.01          0.60      0.39                                           D      0.01          0.01      0.98                                           E      0.60          0.01      0.39                                           ______________________________________                                    

where "p" is an integer corresponding to the number of elements "El" inthe (El_(w) Al_(x) P_(y) Si_(z))O₂ constituent.

The "ELAPSO" molecular sieves are also described as crystallinemolecular sieves having three dimensional microporous frameworkstructures of ELO₂, AlO₂, SiO₂ and PO₂ tetrahedral oxide units andhaving an empirical chemical composition on an anhydrous basis expressedby the formula:

    mR:(EL.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (EL_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; "EL" represents at least one element capable offorming a framework tetrahedral oxide and is selected from the groupconsisting of arsenic, beryllium, boron, chromium, cobalt, gallium,germanium, iron, lithium, magnesium, manganese, titanium and zinc; and"w", "x", "y" and "z" represent the mole fractions of "EL", aluminum,phosphorus and silicon, respectively, present as tetrahedral oxides,said mole fractions being within the limiting compositional values orpoints as follows:

    ______________________________________                                        Mole Fraction                                                                 Point  x             y         (z + w)                                        ______________________________________                                        a      0.60          0.39- (0.01)p                                                                           0.01(p + 1)                                    b      0.39- (0.01p) 0.60      0.01(p + 1)                                    c      0.10          0.55      0.35                                           d      0.55          0.10      0.35                                           ______________________________________                                    

where "p" is as above defined.

The "ELAPSO" molecular sieves include numerous species which areintended herein to be within the scope of the term "non-zeoliticmolecular sieves" such being disclosed in the following copending andcommonly assigned applications, incorporated herein by reference thereto[(A) following a serial number indicates that the application isabandoned, while (CIP) following a serial number indicates theapplication is a continuation-in-part of the immediately precedingapplication and (C) indicates that the application is a continuation ofthe immediately preceding application]:

    ______________________________________                                        U.S. Ser. No.                                                                              Filed         NZMS                                               ______________________________________                                        599,808(A)   April 13, 1984                                                                              AsAPSO                                             845,484(CIP) March 31, 1986                                                                              AsAPSO                                             600,177(A)   April 13, 1984                                                                              BAPSO                                              845,255(CIP) March 28, 1986                                                                              BAPSO                                              600,176(A)   April 13, 1984                                                                              BeAPSO                                             841,752(CIP) March 20, 1986                                                                              BeAPSO                                             599,830(A)   April 13, 1984                                                                              CAPSO                                              852,174(CIP) April 15, 1986                                                                              CAPSO                                              599,925(A)   April 13, 1984                                                                              GaAPSO                                             845,985(CIP) March 31, 1986                                                                              GaAPSO                                             599,971(A)   April 13, 1984                                                                              GeAPSO                                             852,175(CIP) April 15, 1986                                                                              GeAPSO                                             599,952(A)   April 13, 1984                                                                              LiAPSO                                             847,227(CIP) April 2, 1986 LiAPSO                                             600,179      April 13, 1984                                                                              TiAPSO                                             (now U.S. Pat. No. 4,684,617 issued August 4, 1987)                           049,274(C)   May 13, 1987  TiAPSO                                             600,180      April 13, 1984                                                                              MgAPSO                                             600,175      April 13, 1984                                                                              MnAPSO                                             (now U.S. Pat. No. 4,686,092 issued August 11, 1987)                          600,174      April 13, 1984                                                                              CoAPSO                                             600,170      April 13, 1984                                                                              ZnAPSO                                             600,173      April 13, 1984                                                                              FeAPSO                                             (now U.S. Pat. No. 4,683,217 issued July 28, 1987)                            600,168(A)   April 13, 1984                                                                              QuinAPSO                                           063,791(C)   June 22, 1987 QuinAPSO                                           600,181      April 13, 1984                                                                              QuinAPSO                                           600,182      April 13, 1984                                                                              CoMnMgAPSO                                         057,648(C)   June 9, 1987  CoMnMgAPSO                                         600,183      April 13, 1984                                                                              SenAPSO                                            ______________________________________                                    

The disclosures of the patents listed in the foregoing table are hereinincorporated by reference.

TiAPSO MOLECULAR SIEVES

As already mentioned, the TiAPSO molecular sieves are described in U.S.Pat. No. 4,684,617 (incorporated herein by reference); these TiAPSOmolecular sieves are also described in U.S. Ser. No. 049,274, filed May13, 1987.

MgAPSO MOLECULAR SIEVES

The MgAPSO molecular sieves of U.S. Ser. No. 600,180, filed Apr. 13,1984 have three dimensional microporous framework structures of MgO₂ ⁻²,AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units and have an empiricalchemical composition on an anhydrous basis expressed by the formula:

    mR:(Mg.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Mg_(w) Al_(x) P_(y) Si_(z))O₂ and has a value fromzero (0) to about 0.3; and "w", "x", "y" and "z" represent the molefractions of magnesium, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each preferably has a value of atleast 0.01. The mole fractions "w", "x", "y" and "z" are generallydefined as being within the limiting compositional values or points asfollows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.39         0.59   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the MqAPSO molecular sieves the values "w","x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.55         0.43   0.02                                             b        0.43         0.55   0.02                                             c        0.10         0.55   0.35                                             d        0.55         0.10   0.35                                             ______________________________________                                    

MgAPSO compositions are generally synthesized by hydrothermalcrystallization for an effective time at effective pressures andtemperatures from a reaction mixture containing reactive sources ofmagnesium, silicon, aluminum and phosphorus, an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and may be an alkali or other metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C. until crystals of the MgAPSO product are obtained,usually a period of from several hours to several weeks. Generally, thecrystallization period will be from about 2 hours to about 30 days withit typically being from about 4 hours to about 20 days for obtainingMgAPSO crystals. The product is recovered by any convenient method suchas centrifugation or filtration.

In synthesizing the MgAPSO compositions, it is preferred to employreaction mixture compositions expressed in terms of the molar ratios asfollows:

    aR:(Mg.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and can have a value within the range of from zero(0) to about 6 and is more preferably an effective amount greater thanzero to about 6; "b" has a value of from zero (0) to about 500,preferably between about 2 and about 300; and "w", "x", "y" and "z"represent the mole fractions of magnesium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing magnesium,aluminum, phosphorus and silicon as framework tetrahedral oxides areprepared as follows:

Preparative Reagents

MgAPSO compositions are prepared using numerous reagents. Typicalreagents which may be employed to prepare MgAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea for hydrated pseudoboehmite;

(c) LUDOX LS: Trademark of DuPont for an aqueous solution of 30 weightpercent SiO₂ and 0.1 weight percent Na₂ O;

(d) Mg(Ac)₂ : magnesium acetate tetrahydrate, Mg(C₂ H₃ O₂.4H₂ O;

(e) H₃ PO₄ : 85 weight percent aqueous phosphoric acid in water;

(f) TBAOH: tetrabutylammonium hydroxide (40 wt. % in water);

(g) Pr₂ NH: di-n-propylamine;

(h) Pr₃ NH: tri-n propylamine;

(i) Quin: Quinuclidine;

(j) MQuin: Methyl Quinuclidine hydroxide, (17.9%) in water);

(k) C-hex: cyclohexylamine;

(l) TEAOH: tetraethylammonium hydroxide (40 wt. % in water);

(m) DEEA: Diethylethanolamine;

(n) i-Pr₂ NH: di-isopropylamine;

(o) TEABr: tetraethylammonium bromide; and

(p) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water).

Preparative Procedures

The MgAPSO compositions may be prepared by preparing reaction mixtureshaving a molar composition expressed as:

    eR:fMgO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :qSiO.sub.2 :jH.sub.2 O

wherein e, f, g, h, i and j represent the moles of template R, magnesium(expressed as the oxide), SiO₂, Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂O₅) and H₂ O, respectively.

The reaction mixtures may be prepared by the following representativeprocedures, designated hereinafter as Methods A, B and C.

Method A

The reaction mixture is prepared by mixing the ground aluminum source(alipro or CATAPAL) with the H₃ PO₄ and water on a gradual basis withoccasional cooling with an ice bath. The resulting mixture is blendeduntil a homogeneous mixture is observed. When the aluminum source isCATAPAL the water and H₃ PO₄ are first mixed with the CATAPAL addedthereto. The magnesium acetate is dissolved in a portion of the waterand is then added followed by addition of the LUDOX-LS. The combinedmixture is blended until a homogeneous mixture is observed. The organictemplating agent is added to this mixture and blended until ahomogeneous mixture is observed. The resulting mixture (final reactionmixture) is placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C. or 200° C.) foran effective time. Alternatively, if the digestion temperature is 100°C. the final reaction mixture is placed in a lined(polytetrafluoroethylene) screw top bottle for a time. Digestions aretypically carried out under autogenous pressure. The products areremoved from the reaction vessel, cooled and evaluated as set forthhereinafter.

Method B

When method B is employed the organic templating agent isdi-n-propylamine. The aluminum source, silicon source and one-half ofthe water are first mixed and blended until a homogeneous mixture isobserved. A second solution was prepared by mixing the remaining water,the H₃ PO₄ and the magnesium acetate. This solution is then added to theabove mixture. The magnesium acetate and H₃ PO₄ solution is then addedto the above mixture and blended until a homogeneous mixture isobserved. The organic templating agent(s) is/are then added and theresulting reaction mixture digested and product recovered as in MethodA.

Method C

Method C is carried out by mixing aluminum isopropoxide, LUDOX-LS andwater in a blender or by mixing water and aluminum iso-propoxide in ablender followed by addition of the LUDOX-LS. H₃ PO₄ and magnesiumacetate are then added to the resulting mixture. The organic templatingagent is then added to the resulting mixture and digested and productrecovered as in Method A.

MnAPSO MOLECULAR SIEVES

As already mentioned, the MnAPSO molecular sieves are described in U.S.Pat. No. 4,686,092 issued Aug. 11, 1987 (incorporated herein byreference).

CoAPSO MOLECULAR SIEVES

The CoAPSO molecular sieves of U.S. Ser. No. 600,174, filed Apr. 13,1984 have three-dimensional microporous framework structures of CoO₂ ⁻²,AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units and have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.2 Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to a 0.3; and "w", "x", "y" and "z" represent the molefractions of cobalt, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides, where the mole fractions "w", "x", "y"and "z" are each at least 0.01 and are generally defined, as beingwithin the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the CoAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.55         0.43   0.02                                             b        0.43         0.55   0.02                                             c        0.10         0.55   0.35                                             d        0.55         0.10   0.35                                             ______________________________________                                    

CoAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofcobalt, silicon, aluminum and phosphorus, an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and optionally an alkali metal. The reactionmixture is generally placed in a sealed pressure vessel, preferablylined with an inert plastic material such as polytetrafluoroethylene andheated, preferably under autogenous pressure at an effective temperaturewhich is generally between 50° C. and 250° C. and preferably between100° C. and 200° C. until crystals of the CoAPSO product are obtained,usually for an effective time of from several hours to several weeks.Generally the effective crystallization time will be from about 2 hoursto about 30 days and typically from about 4 hours to about 20 days. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the CoAPSO, it is preferred to employ a reaction mixturecomposition expressed in terms of the molar ratios as follows:

    aR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and 300; and "w", "x", "y" and "z" represent the molefractions of cobalt, aluminum, phosphorus and silicon, respectively, andeach has a value of at least 0.01. In a preferred embodiment thereaction mixture is selected such that the mole fractions "w", "x", "y"and "z" are generally defined as being within the limiting compositionalvalues or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing cobalt, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

CoAPSO compositions may be prepared using numerous reagents. Reagentswhich may be employed to prepare CoAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for pseudoboemite;

(c) LUDOX-LS: Trademark of DuPont for an aqueous solution of 30 weightpercent SiO₂ and 0.1 weight percent Na₂ O;

(d) Co(Ac)₂ cobalt acetate, Co(C₂ H₃ O₂)₂.4H₂ O;

(e) CoSO₄ : cobalt sulfate, (CoSO₄.7 H₂ O);

(f) H₃ PO₄ : 85 weight percent phosphoric acid in water;

(g) TBAOH: tetrabutylammonium hydroxide (25 wt % in methanol):

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH)

(l) C-hex: cyclohexylamine;

(m) TEAOH: tetraethylammonium hydroxide (40 wt. % in water);

(n) DEEA: diethanolamine;

(o) TPAOH: tetrapropylammonium hydroxide (40 wt. % in water); and

(p) TMAOH: tetramethylammonium hydroxide (40 wt. % in water).

Preparative Procedure

CoAPSO compositions may be prepared by preparing reaction mixtureshaving a molar composition expressed as:

    eR:fCoO:hAl.sub.2 O.sub.3 :iP.sub.2 O.sub.5 :gSiO.sub.2 :jH.sub.2 O

wherein e, f, h, i, g and j represent the moles of template R, cobalt(expressed as the oxide), Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅),SiO₂ and H₂ O, respectively.

The reaction mixtures are prepared by forming a starting reactionmixture comprising the H₃ PO₄ and one half of the water. This mixture isstirred and the aluminum source (Alipro or CATAPAL) added. The resultingmixture is blended until a homogeneous mixture is observed. The LUDOX-LSis then added to the resulting mixture and the new mixture blended untila homogeneous mixture is observed. The cobalt source (e.g., Co(Ac)₂,Co(SO₄) or mixtures thereof) is dissolved in the remaining water andcombined with the first mixture. The combined mixture is blended until ahomogeneous mixture is observed. The organic templating agent is addedto this mixture and blended for about two to four minutes until ahomogeneous mixture is observed. The resulting mixture (final reactionmixture) is placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C., 200° C. or 225°C.) for a time. Digestions are typically carried out at the autogenouspressure. The products are removed from the reaction vessel and cooled.

ZnAPSO MOLECULAR SIEVES

The ZnAPSO molecular sieves of U.S. Ser. No. 600,170, filed Apr. 13,1984 comprise framework structures of ZnO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂tetrahedral units having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(Zn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Zn_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of zinc, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides and each has a value of at least 0.01. Themole fractions "w", "x", "y" and "z" are generally defined being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of ZnAPSO molecular sieves the values "w", "x","y" and "z" in the above formula are within the limiting compositionalvalues or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.55         0.43   0.02                                             b        0.43         0.55   0.02                                             c        0.10         0.55   0.35                                             d        0.55         0.10   0.35                                             ______________________________________                                    

ZnAPSO compositions are generally synthesized by hydrothermalcrystallization at effective process conditions from a reaction mixturecontaining active sources of zinc, silicon, aluminum and phosphorus,preferably an organic templating, i.e., structure directing, agent,preferably a compound of an element or Group VA of the Periodic Table,and/or optionally an alkali or other metal. The reaction mixture isgenerally placed in a sealed pressure vessel, preferably lined with aninert plastic material such as polytetrafluoroethylene and heated,preferably under autogenous pressure, at a temperature between 50° C.and 250° C., and preferably between 100° C. and 200° C. until crystalsof the ZnAPSO product are obtained, usually a period of from severalhours to several weeks. Generally the effective crystallization periodis from about 2 hours to about 30 days with typical periods of fromabout 4 hours to about 20 days being employed to obtain ZnAPSO products.The product is recovered by any convenient method such as centrifugationor filtration.

In synthesizing the ZnAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Zn.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, morepreferably between about 2 and about 300; and "w", "x", "y" and "z"represent the mole fractions of zinc, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01. In a preferredembodiment the reaction mixture is selected such that the mole fractions"w", "x", "y" and "z" are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing zinc, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

ZnAPSO compositions are typically prepared numerous reagents. Reagentswhich may be employed to prepare ZnAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the trade name of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) ZnAc: Zinc Acetate, Zn(C₂ H₃ O₂)₂.4H₂ O;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) TMAOH: Tetramethylammonium hydroxide pentahydrate, (CH₃)₄ NOH.5H₂ O;

(i) TPAOH: 40 weight percent aqueous solution of tetrapropylammoniumhydroxide, (C₃ H₄)₄ NOH;

(j) Pr₂ NH: Di-n-propylamine, (C₃ H₄)₂ NH;

(k) Pr₃ N: Tri-n propylamine, (C₃ H₇)₃ N;

(l) Quin: Quinuclidine, (C₇ H₁₃ N);

(m) C-hex: cyclohexylamine; and

(n) DEEA: diethylethanolamine, (C₂ H₅)₂ NC₂ H₅ OH.

Preparative Procedure

ZnAPSO compositions are typically prepared by forming reaction mixtureshaving a molar composition expressed as:

    eR:fZnO:qAl.sub.2 O.sub.3 :hP.sub.2 O.sub.5 :iSiO.sub.2 :jH.sub.2 O

wherein e, f, q, h, i and j represent the moles of template R, zinc(expressed as the oxide), Al₂ O₃, P₂ O₅ (H₃ PO₄ expressed as P₂ O₅),SiO₂ and H₂ O, respectively.

The reaction mixtures are generally prepared by forming a startingreaction mixture comprising the H₃ PO₄ and a portion of the water. Thismixture is stirred and the aluminum source added. The resulting mixtureis blended until a homogeneous mixture is observed. The LUDOX LS is thenadded to the resulting mixture and the new mixture blended until ahomogeneous mixture is observed. The zinc source (zinc acetate) isdissolved in the remaining water and combined with the first mixture.The combined mixture is blended until a homogeneous mixture is observed.The organic templating agent is added to this mixture and blended forabout two to four minutes until a homogeneous mixture is observed. Theresulting mixture (final reaction mixture) is placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat an effective temperature for an effective time. Digestions aretypically carried out under autogenous pressure. The products areremoved from the reaction vessel and cooled.

FeAPSO MOLECULAR SIEVES

As already mentioned, the FeAPSO molecular sieves are described in U.S.Pat. No. 4,683,217 (incorporated herein by reference).

QUINARY MOLECULAR SIEVES

The QuinAPSO quinary molecular sieves of U.S. Ser. Nos. 600,168 and600,181, both filed Apr. 13, 1984, have three dimensional microporousframework structures of MO₂ ^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedralunits, where "n" is -3, -2, -1, 0 or +1, and have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero (0) to about 0.3; M represents at least two elements selectedfrom the group consisting of arsenic, beryllium, boron, chromium,cobalt, gallium, germanium, iron, lithium, magnesium, manganese,titanium, vanadium and zinc; and "w", "x", "y" and "z" represent themole fractions of M, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides. Preferably, M represents the combinationof cobalt and manganese. The mole fractions "w", "x", "y", and "z" aregenerally defined as being within the limiting Compositional values orpoints as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.37   0.03                                             B        0.37         0.60   0.03                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

Preferably the mole fractions w, x, y, and z will fall within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.60         0.37   0.03                                             b        0.37         0.60   0.03                                             c        0.01         0.60   0.39                                             d        0.01         0.39   0.60                                             e        0.39         0.01   0.60                                             f        0.60         0.01   0.39                                             ______________________________________                                    

QuinAFSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofthe elements M, aluminum, phosphorus and silicon and preferably anorganic templating agent, i.e., structure-directing, agent. Thestructure-directing agents are preferably a compound of an element ofGroup VA of the Periodic Table, and may be an alkali or other metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureand at typical effective temperatures between 50° C. and 250° C.,preferably between 100° C. and 200° C., until crystals of the QuinAPSOproduct are obtained, usually over a period of from several hours toseveral weeks. Typical effective crystallization times are from about 2hours to 30 days with from about 4 hours to about 20 days beinggenerally employed to obtain QuinAPSO products. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the QuinAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "w", "x", "y" and "z" represent themole fractions of elements M, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.37   0.03                                             G        0.37         0.60   0.03                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. QuinAPSO compositions were prepared usingnumerous regents; the appropriate sources of the various elements M arethe same as those used in the preparation of the various APO and APSOmolecular sieves containing the same elements, as described in detailabove and below.

Reagents which may be employed to prepare QuinAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent of Na₂ O;

(c) H₃ PO₄ : 85 weight percent phosphoric acid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂.4H₂ O (for QuinAPSOscontaining manganese);

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂.4H₂ O (for QuinAPSOs containingcobalt);

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide; and

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

Preparative Procedures

QuinAPSOs may be prepared by forming a starting reaction mixture byadding H₃ PO₄ and one half of the quantity of water. To this mixture analuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture a silica (e.g.,LUDOX-LS) is added and the resulting mixture blended (about 2 minutes)until a homogeneous mixture is observed. A second mixture is preparedusing manganese acetate (or a appropriate source of another element M)and one half of the remaining water. A third mixture is prepared usingcobalt acetate (or a appropriate source of another element M) and onehalf of the remaining water. The three mixtures are admixed and theresulting mixture blended until a homogeneous mixture is observed. Theorganic templating agent is then added to the resulting mixture and theresulting mixture blended until a homogeneous mixture is observed, i.e.,about 2 to 4 minutes. The pH of the mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat an effective temperature for an effective time. Digestions aretypically carried out under autogeneous pressure.

CoMnMgAPSO MOLECULAR SIEVES

The CoMnMgAPSO senary molecular sieves of U.S. Ser. No. 600,182, filedApr. 13, 1984, and of U.S. Ser. No. 057,648 filed June 9, 1987, havethree-dimensional microporous framework structures of CoO₂ ⁻², MnO₂ ⁻²,MgO₂ ⁻², AlO₂, PO₂ and SiO₂ tetrahedral oxide units having an empiricalchemical composition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(t) Mn_(u) Mg_(v) Al_(x) P_(y) Si_(z))O₂ and hasa value of from zero (0) to about 0.3; "t", "u", "v", "x", "y" and "z"represent the mole fractions of cobalt, manganese, magnesium, aluminum,phosphorus and silicon, respectively, present as tetrahedral oxides andeach has a value of at least 0.01. The mole fractions "w", "x", "y" and"z", where "w" is the sum of "t"+"u"+"v", are generally defined as beingwithin the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.36   0.04                                             B        0.36         0.60   0.04                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the CoMnMgAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.55         0.41   0.04                                             b        0.41         0.55   0.04                                             c        0.10         0.55   0.35                                             d        0.55         0.10   0.35                                             ______________________________________                                    

CoMnMgAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofcobalt, manganese, magnesium, aluminum, phosphorus and silicon, andpreferably an organic templating agent, i.e., structure-directing agent.The structure-directing agents are preferably a compound of an elementof Group VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C., until crystals of the CoMnMgAPSO product are obtained,usually over a period of from several hours to several weeks. Typicalcrystallization times are from about 2 hours to about 30 days with fromabout 4 hours to about 20 days generally being employed to obtainCoMnMgAPSO products. The product is recovered by any convenient methodsuch as centrifugation or filtration.

In synthesizing the CoMnMgAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(Co.sub.t Mn.sub.u Mg.sub.v Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6 and more preferably from greater than zero to about 2; "b"has a value of from zero (0) to about 500, preferably between about 2and about 300; and "t", "u", "v", "x", "y", and "z" represent the molefractions of cobalt, manganese, magnesium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In a preferred embodiment the reaction mixture is selected such that themole fractions "w", "x", "y" and "z", where "w" is the sum of"t"+"u"+"v", are generally defined as being within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.36   0.04                                             G        0.36         0.60   0.04                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "t", "u", "v", "x", "y" and"z" such that (t+u+v+x+y+z)=1 00 mole. Molecular sieves containingcobalt, manganese, magnesium, aluminum, phosphorus and silicon asframework tetrahedral oxide units are prepared as follows:

Preparative Reagents

CoMnMgAPSO compositions may be prepared by using numerous reagents.Reagents which may be employed to prepare CoMnMgAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(c) H₃ PO₄ : aqueous solution which is 85 weight percent phosphoricacid;

(d) MnAc: Manganese acetate, Mn(C₂ H₃ O₂)₂.4H₂ O;

(e) CoAc: Cobalt Acetate, Co(C₂ H₃ O₂)₂.4H₂ O;

(f) MgAc: Magnesium Acetate Mg(C₂ H₃ O₂).4H₂ O;

(g) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide; and

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH.

Preparative Procedures

CoMnMgAPSOs may be prepared by forming a starting reaction mixture byadding H₃ PO₄ and one half of the quantity of water. To this mixture analuminum isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture a silica (e.g.,LUDOX-LS) is added and the resulting mixture blended (about 2 minutes)until a homogeneous mixture is observed.

Three additional mixtures are prepared using cobalt acetate, magnesiumacetate and manganese acetate using one third of the remainder of thewater for each mixture. The four mixtures are then admixed and theresulting mixture blended until a homogeneous mixture is observed. Anorganic templating agent is then added to the resulting mixture and theresulting mixture blended until a homogeneous mixture is observed, i.e.,about 2 to 4 minutes. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature for a time. Digestions are typically carried out underautogenous pressure.

SenAPSO MOLECULAR SIEVES

The SenAPSO molecular sieves of U.S. Ser. No. 600,183, filed Apr. 13,1984 have three-dimensional microporous framework structures of MO₂^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral oxide units, where "n" is -3,-2, -1, 0 or +1, and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of"R"present per mole of (M_(w) Al_(x) P_(y) Si_(z))O₂, and has a value offrom zero to about 0.3; "M" represents three elements selected from thegroup consisting of arsenic, beryllium, boron, chromium, cobalt,gallium, germanium, iron, lithium, magnesium, manganese, titanium,vanadium and zinc; "n" may have the aforementioned values depending uponthe oxidation state of "M"; and "w", "x", "y" and "z" represent the molefractions of elements "M", aluminum, phosphorus and silicon,respectively, present as tetrahedral oxides. The mole fractions "w","x", "y" and "z" are generally defined as being within the limitingcompositional values or points as follows, wherein "w" denotes thecombined mole fractions of the three elements "M" such that "w"="w₁"+"w₂ "+"w₃ " and each element "M" has a mole fraction of at least 0.01:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.36   0.04                                             B        0.36         0.60   0.04                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the SenAPSO molecular sieves the values of"w", "x", "y" and "z" in the above formula are within the limitingcompositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.60         0.36   0.04                                             b        0.36         0.60   0.04                                             c        0.01         0.60   0.39                                             d        0.01         0.39   0.60                                             e        0.39         0.01   0.60                                             f        0.60         0.01   0.39                                             ______________________________________                                    

SenAPSO composition are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofelements "M", aluminum, phosphorus and silicon, and preferably anorganic templating, i.e., structure-directing, agent. The structuredirecting agents are preferably a compound of an element of Group VA ofthe Periodic Table, and/or optionally an alkali or other metal. Thereaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between 50° C. and 250° C., and preferably between 100°C. and 200° C., until crystals of the SenAPSO product are obtained,usually over a period of from several hours to several weeks. Typicalcrystallization times are from about 2 hours to about 30 days with fromabout 4 hours to about 20 days generally being employed to obtainSenAPSO products. The product is recovered by any convenient method suchas centrifugation or filtration.

In synthesizing the SenAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(M.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6 and more preferably from greater than zero to about 2; "b"has a value of from zero (0) to about 500, preferably between about 2and about 300; and "w", "x", "y", and "z" represent the mole fractionsof elements "M", aluminum, phosphorus and silicon, respectively, andeach has a value of at least 0.01, with the proviso that each "M" ispresent in a mole fraction of at least 0.01.

In a preferred embodiment the reaction mixture is selected such that themole fractions "w", "x", "y" and "z" are generally defined as beingwithin the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.36   0.04                                             G        0.36         0.60   0.04                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. The SenAPSO molecular sieves are prepared bypreparative techniques, and using sources of the elements "M" similar tothose described for the other APSO molecular sieves described above andbelow.

AsAPSO MOLECULAR SIEVES

The AsAPSO molecular sieves of U.S. Ser. No. 599,808, filed Apr. 13,1984, and U.S. Ser. No. 845,484 filed Mar. 31, 1986 have a frameworkstructure of AsO₂ ^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units havingan empirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(As.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (As_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements arsenic,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the AsAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.60         0.38   0.02                                             b        0.38         0.60   0.02                                             c        0.01         0.60   0.39                                             d        0.01         0.39   0.60                                             e        0.39         0.01   0.60                                             f        0.60         0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the AsAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        g        0.50         0.40   0.10                                             h        0.42         0.48   0.10                                             i        0.38         0.48   0.14                                             j        0.38         0.37   0.25                                             k        0.45         0.30   0.25                                             l        0.50         0.30   0.20                                             ______________________________________                                    

AsAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofarsenic, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theAsAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 12 hours to about 10 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the AsAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(As.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.0; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 60; and "w", "x", "y" and "z"represent the mole fractions of arsenic, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

Especially preferred reaction mixtures are those containing from about 1to about 2 total moles of silicon and arsenic, and from about 1 to about2 moles of aluminum, per mole of phosphorus.

In the foregoinq expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing arsenic, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

AsAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare AsAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) As₂ O₅, arsenic (V) oxide;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol; Tetraalkylorthosilicates, such astetraethylorthosilicate.

Preparative Procedures

AsAPSOs may be prepared by forming a starting reaction mixture bydissolving the arsenic (V) oxide and the H₃ PO₄ in at least part of thewater. To this solution the aluminum isopropoxide or CATAPAL is added.This mixture is then blended until a homogeneous mixture is observed. Tothis mixture the templating agent and then the silica is added and theresulting mixture blended until a homogeneous mixture is observed. Themixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

BAPSO MOLECULAR SIEVES

The BAPSO molecular sieves of U.S. Ser. No. 600,177, filed Apr. 13,1984, and U.S. Ser. No. 845,255 filed Mar. 28, 1986 have a frameworkstructure of BO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (B.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (B_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements boron,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the BAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.60         0.38   0.02                                             b        0.38         0.60   0.02                                             c        0.01         0.60   0.39                                             d        0.01         0.39   0.60                                             e        0.39         0.01   0.60                                             f        0.60         0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the BAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        g        0.51         0.42   0.07                                             h        0.45         0.48   0.07                                             i        0.33         0.48   0.19                                             j        0.33         0.38   0.29                                             k        0.36         0.35   0.29                                             l        0.51         0.35   0.14                                             ______________________________________                                    

BAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofboron, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theBAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the BAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (B.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of boron, aluminum, phosphorus and silicon,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.38   0.02                                            G        0.38          0.60   0.02                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from about1.0 to about 2 total moles of silicon and boron, and from about 0.75 toabout 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w" , "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing boron, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

BAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare BAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) H₃ BO₃, boric acid, and trialkyl borates;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(q) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

n(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

Preparative Procedures

BAPSOs may be prepared by forming a starting reaction mixture bydissolving aluminum isopropoxide in an alcohol such as isopropanol,adding the H₃ PO₄ and recovering the solid which precipitates. Thissolid is then added to water, and trialkylborate (for example trimethylborate) added, followed by silica and the templating agent. This mixtureis then blended until a homogeneous mixture is observed. The mixture isthen placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C. or 200° C.) for atime or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autoqenous pressure.

BeAPSO MOLECULAR SIEVES

The BeAPSO molecular sieves of U.S. Ser. No. 600,176, filed Apr. 13,1984, and U.S. Ser. No. 841,752 filed Mar. 20, 1986 have a frameworkstructure of BeO₂ ⁻², AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Be.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Be_(w) Al_(x) P_(y) Si_(x))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements beryllium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the BeAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

BeAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofberyllium, silicon, aluminum and phosphorus, preferrably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C and about 250° C, andpreferably between about 100° C and about 200° C, until crystals of theBeAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, have been observed, withfrom 1 to 10 days being preferred. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the BeAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Be.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 to about 300,most preferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of beryllium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.38   0.02                                            G        0.38          0.60   0.02                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing beryllium,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

Preparative Reagents

BeAPSO compositions may be prepared by numerous reagents. Reagents whichmay be employed to prepare BeAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) beryllium sulfate, BeSO₄ ;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

Preparative Procedures

BeAPSOs may be prepared by forming a starting solution by mixing H₃ PO₄in at least part of the water. To this solution is added berylliumsulfate (or another beryllium salt) and the resultant mixture stirreduntil a homogeneous solution is obtained. To this solution may be addedsuccessively the aluminum oxide, the silica and the templating agent,with the mixture being stirred between each addition until it ishomogeneous. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autoqenous pressure.

CAPSO MOLECULAR SIEVES

The CAPSO molecular sieves of U.S. Ser. No. 599,830, filed Apr. 13,1984, and U.S. Ser. No. 852,174 filed Apr, 15, 1986 have a frameworkstructure of CrO₂ ^(n), AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units (where"n" is -1, 0 or +1) having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR: (Cr.sub.w Al.sub.x P.sub.y Si.sub.x)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Cr_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements chromium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the CAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

In an especially preferred subclass of the CAPSO molecular sieves, thevalues of x and y in the above formula are each within the range ofabout 0.4 to 0.5 and (z+w) is in the range of about 0.02 to 0.15.

Since the exact nature of the CAPSO molecular sieves is not clearlyunderstood at present, although all are believed to contain CrO₂tetrahedra in the three dimensional microporous crystal frameworkstructure, it is advantageous to characterize the CAPSO molecular sievesby means of their chemical composition. This is due to the low level ofchromium present in certain of the CAPSO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between chromium, aluminum, phosphorus and silicon. As aresult, although it is believed that CrO₂ tetrahedra are substitutedisomorphously for AlO₂, PO₂ or SiO₂ tetrahedra, it is appropriate tocharacterize certain CAPSO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

CAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofchromium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C., until crystals ofthe CAPSO product are obtained, usually a period of from several hoursto several weeks. Typical effective times of from 2 hours to about 30days, generally from about 4 hours to about 20 days, and preferablyabout 1 to about 10 days, have been observed. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the CAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Cr.sub.w Al.sub.x P.sub.y Si.sub.x)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of chromium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.38   0.02                                            G        0.38          0.60   0.02                                            H        0.01          0.60   0 39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.3 to about 0.5 total moles of silicon and chromium, and from about0.75 to about 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing chromium,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

Preparative Reagents

CAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare CAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) chromium acetate, and chromium acetate hydroxide;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

Preparative Procedures

CAPSOs may be prepared by forming a starting solution by dissolving H₃PO₄ in at least part of the water. To this solution the aluminumisopropoxide is added. This mixture is then blended until a homogeneousmixture is observed. To this mixture the silica, the chromium acetate orchromium acetate hydroxide and the templating agent are successivelyadded and at each step the resulting mixture is blended until ahomogeneous mixture is observed.

Alternatively, the water and aluminum isopropoxide may first be mixed,and then the silica, the chromium acetate or chromium acetate hydroxide,the phosphoric acid and the templating agent added, and again at eachstep the resulting mixture is blended until a homogeneous mixture isobserved.

In either case, the mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autogenous pressure.

GaAPSO MOLECULAR SIEVES

The GaAPSO molecular sieves of U.S. Ser. No. 599,925, filed Apr. 13,1984, and U.S. Ser. No. 845,985 filed Mar. 31, 1986 have a frameworkstructure of GaO₂ ⁻, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of Ga_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.2; and "w", "x","y" and "z" represent the mole fractions of the elements gallium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the GaAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0.39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

In an especially preferred subclass of the GaAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        g        0.45          0.40   0.15                                            h        0.33          0.52   0.15                                            i        0.20          0.52   0.28                                            j        0.20          0.45   0.35                                            k        0.36          0.29   0.35                                            1        0.45          0.29   0.26                                            ______________________________________                                    

GaAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgallium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C., until crystals ofthe GaAPSO product are obtained, usually a period of from several hoursto several weeks. Typical effective times of from 2 hours to about 30days, generally from about 4 hours to about 20 days, and preferablyabout 2 to about 15 days, have been observed. The product is recoveredby any convenient method such as centrifugation or filtration.

In synthesizing the GaAPSO compositions, it is preferred to employ areaction mixture

composition expressed in terms of the molar ratios as follows:

    aR: (Ga.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.0; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "w", "x", "y" and "z"represent the mole fractions of gallium, aluminum, phosphorus andsilicon, respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        F        0.60          0.38   0.02                                            G        0.38          0.60   0.02                                            H        0.01          0.60   0.39                                            I        0.01          0.01   0.98                                            J        0.60          0.01   0.39                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.5 to about 1.0 total moles of silicon and gallium, and from about 0.75about 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing gallium, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

GaAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GaAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite:

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) gallium hydroxide, or gallium sulfate;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

Preparative Procedures

GaAPSOs may be prepared by forming a starting solution by dissolving H₃PO₄ in at least part of the water. To this solution the aluminumhydroxide or isopropoxide is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture is added a secondsolution prepared by adding silica to a solution containing the galliumhydroxide and the templating agent and then the combined mixture isblended until a homogeneous mixture is observed.

Alternatively, the templating agent may be added to the solutioncontaining the phosphoric acid and water, and a solution of galliumsulfate in water added, followed by successive additions of silica andaluminum oxide and then the combined mixture is blended until ahomogeneous mixture is observed.

In either case, the mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autogenous pressure.

GeAPSO MOLECULAR SIEVES

The GeAPSO molecular sieves of U.S. Ser. No. 599,971, filed Apr 13,1984, and U.S. Ser. No. 852,175 filed Apr. 15, 1986 have a frameworkstructure of GeO₂, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ge_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements geranium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limited compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        A        0.60          0.38   0.02                                            B        0.38          0.60   0.02                                            C        0.01          0.60   0.39                                            D        0.01          0.01   0.98                                            E        0.60          0.01   0.39                                            ______________________________________                                    

In a preferred subclass of the GeAPSO molecular sieves, the values of w,x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        a        0.60          0.38   0.02                                            b        0.38          0.60   0.02                                            c        0.01          0.60   0 39                                            d        0.01          0.39   0.60                                            e        0.39          0.01   0.60                                            f        0.60          0.01   0.39                                            ______________________________________                                    

In an especially preferred subclass of the GeAPSO molecular sieves, thevalues of w, x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      (z + w)                                         ______________________________________                                        g        0.60          0.35   0.05                                            h        0.47          0.48   0.05                                            i        0.40          0.48   0.12                                            j        0.40          0.36   0.24                                            k        0.46          0.30   0.24                                            l        0.60          0.30   0.10                                            ______________________________________                                    

GeAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgeranium, silicon, aluminum and phosphorus, preferably an inorganictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed on asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C., until crystals ofthe GeAPSO product are obtained, usually a period of from several hoursto several weeks. Typical effective times of from 2 hours to about 30days, generally from about 4 hours to about 20 days, and preferablyabout 12 hours to about 7 days have been observed. The product isrecovered by any convenient method such as centrifugation or filtration.

In synthesizing the GaAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Ge.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and desirably not greaterthan about 10; and "w", "x", "y" and "z" represent the mole fractions ofgermanium, aluminum, phosphorus and silicon, respectively, and each hasa value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.2 to about 0.3 total moles of silicon and germanium, and from about0.75 about 1.25 moles of aluminum, per mole of phosphorus.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing germanium,aluminum, phosphorus and silicon as framework tetrahedral oxide unitsare prepared as follows:

Preparative Reagents

GeAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GeAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) germanium tetrachloride or germanium ethoxide;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(q) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide,

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate; and

(q) aluminum chlorhydrol.

Preparative Procedures

In some cases, it may be advantageous, when synthesizing the GeAPSOcompositions, to first combine sources of germanium and aluminum, or ofgermanium, aluminum and silicon, to form a mixed germanium/aluminum orgermanium/aluminum/silicon compound (this compound being typically amixed oxide) and thereafter to combine this mixed compound with a sourceof phosphorus to form the final GeAPSO composition. Such mixed oxidesmay be prepared for example by hydrolyzing aqueous solutions containinggermanium tetrachloride and aluminum chlorhydrol, or germanium ethoxide,tetraethylorthosilicate, and aluminum tri-sec-butoxide.

GeAPSOs may be prepared by forming a starting solution by dissolving H₃PO₄ in at least part of the water. To this solution the aluminumisopropoxide or CATAPAL is added. This mixture is then blended until ahomogeneous mixture is observed. To this mixture is the templating agentand then a solution containing tetraethylorthosilicate and germaniumethoxide, and the resulting mixture blended until a homogeneous mixtureis observed.

Alternatively, the phosphoric acid may first be mixed with thetemplating agent, and then a solution containing tetraethylorthosilicateand germanium ethoxide combined with the phosphoric acid/templatingagent solution. Then the aluminum oxide is added and the resultantmixture blended until homogeneous.

In a third procedure, the phosphoric acid may first be mixed with thetemplating agent and water, and to the resultant solution is added thesolid aluminum/ silicon/germanium mixed oxide prepared as describedabove. The resultant mixture is then blended until homogeneous.

Whichever procedure is adopted, the final mixture is then placed in alined (polytetrafluoroethylene) stainless steel pressure vessel anddigested at a temperature (150° C. or 200° C.) for a time or placed inlined screw top bottles for digestion at 100° C. Digestions aretypically carried out under autogenous pressure.

LiAPSO MOLECULAR SIEVES

The LiAPSO molecular sieves of U.S. Ser. No. 599,952, filed Apr. 13,1984, and U.S. Ser. No. 847,227 filed Apr. 2, 1986 have a frameworkstructure of LiO₂ ⁻³, AlO₂ ⁻, PO₂ ⁺ and SiO₂ tetrahedral units having anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(w) Al_(x) P_(y) Si_(z))O₂ and has a value ofzero to about 0.3, but is preferably not greater than 0.15; and "w","x", "y" and "z" represent the mole fractions of the elements lithium,aluminum, phosphorus and silicon, respectively, present as tetrahedraloxides. The mole fractions "w", "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

In a preferred subclass of the LiAPSO molecular sieves, the values of w,x, y, and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        a        0.60         0.38   0.02                                             b        0.38         0.60   0.02                                             c        0.01         0.60   0.39                                             d        0.01         0.39   0.60                                             e        0.39         0.01   0.60                                             f        0.60         0.01   0.39                                             ______________________________________                                    

In an especially preferred subclass of the LiAPSO molecular sieves, thevalue of w+z is not greater than about 0.20.

Since the exact nature of the LiAPSO molecular sieves is not clearlyunderstood at present, although all are believed to contain LiO₂tetrahedra in the three-dimensional microporous crystal frameworkstructure, it is advantageous to characterize the LiAPSO molecularsieves by means of their chemical composition. This is due to the lowlevel of lithium present in certain of the LiAPSO molecular sievesprepared to date which makes it difficult to ascertain the exact natureof the interaction between lithium, aluminum, phosphorus and silicon. Asa result, although it is believed that LiO₂ tetrahedra are substitutedisomorphously for AlO₂, PO₂ or SiO₂ tetrahedra, it is appropriate tocharacterize certain LiAPSO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

LiAPSO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources oflithium, silicon, aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autoqenouspressure at a temperature between about 50° C. and about 250° C, andpreferably between about 100° C. and about 200° C. until crystals of theLiAPSO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, and preferably about 1 toabout 10 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the LiAPSO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR : (Li.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20, and most desirably notgreater than about 10; and "w", "x", "y" and "z" represent the molefractions of lithium, aluminum, phosphorus and silicon, respectively,and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "w", "x", "y" and "z" are generally defined as being withinthe limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        F        0.60         0.38   0.02                                             G        0.38         0.60   0.02                                             H        0.01         0.60   0.39                                             I        0.01         0.01   0.98                                             J        0.60         0.01   0.39                                             ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "w", "x", "y" and "z" suchthat (w+x+y+z)=1.00 mole. Molecular sieves containing lithium, aluminum,phosphorus and silicon as framework tetrahedral oxide units are preparedas follows:

Preparative Reagents

LiAPSO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare LiAPSOs include:

(a) Alipro: aluminum isopropoxide;

(b) CATAPAL: Trademark of Condea Corporation for hydratedpseudoboehmite;

(c) LUDOX-LS: LUDOX-LS is the tradename of DuPont for an aqueoussolution of 30 weight percent SiO₂ and 0.1 weight percent Na₂ O;

(d) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(e) lithium orthophosphate;

(f) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(g) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(h) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(i) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(j) Quin: Quinuclidine, (C₇ H₁₃ N);

(k) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(l) C-hex: cyclohexylamine;

(m) TMAOH: tetramethylammonium hydroxide;

(n) TPAOH: tetrapropylammonium hydroxide; and

(o) DEEA: 2-diethylaminoethanol;

(p) Tetraalkylorthosilicates, such as tetraethylorthosilicate.

Preparative Procedures

LiAPSOs may be prepared by forming a starting reaction mixture mixinglithium phosphate and aluminum oxide, then adding the resultant mixtureto the H₃ PO₄. To the resultant mixture is added silica and thetemplating agent and the resulting mixture is blended until ahomogeneous mixture is observed. The mixture is then placed in a lined(polytetrafluoroethylene) stainless steel pressure vessel and digestedat a temperature (150° C. or 200° C.) for a time or placed in linedscrew top bottles for digestion at 100° C. Digestions are typicallycarried out under autogenous pressure.

AlPO₄ ALUMINOPHOSPHATE MOLECULAR SIEVES

As already mentioned, the AlPO₄ aluminophosphate molecular sieves aredescribed in U.S. Pat. No. 4,310,440 (incorporated herein by reference);these AlPO₄ molecular sieves are also described in U.S. Ser. No.880,559, filed June 30, 1986.

MeAPO MOLECULAR SIEVES

MeAPO molecular sieves are crystalline microporous aluminophosphates inwhich the substituent metal is one of a mixture of two or more divalentmetals of the group magnesium, manganese, zinc and cobalt and aredisclosed in U.S. Pat. No. 4,567,029 (incorporated herein by reference).

FAPO MOLECULAR SIEVES

As already mentioned, ferroaluminophosphates (FAPO's) are disclosed inU.S. Pat. No. 4,554,143 (incorporated herein by reference).

TAPO MOLECULAR SIEVES

As already mentioned, TAPO molecular sieves are disclosed in U.S. Pat.No. 4,500,561 (incorporated herein by reference).

ELAPO MOLECULAR SIEVES

"ELAPO" molecular sieves are a class of crystalline molecular sieves inwhich at least one element capable of forming a three dimensionalmicroporous framework forms crystal framework structures of AlO₂ ⁻, PO₂⁺ and MO₂ ^(n) tetrahedral oxide units wherein "MO₂ ^(n) " represents atleast one different element (other than Al or P) present as tetrahedraloxide units "Mo₂ ^(n") with charge "n" where "n" may be - 3, -2, -1, 0or +1. The members of this novel class of molecular sieve compositionshave crystal framework structures of AlO₂ ⁻, PO₂ ⁺ and MO₂ ^(n)tetrahedral units and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ ; "M" represents at least onee capable of forming framework tetrahedral oxides; and "x", "y" and "z"represent the mole fraction of "M", aluminum and phosphorus,respectively, present as tetrahedral oxides. "M" is at least onedifferent (i.e., not aluminum, phosphorus or oxygen) element such thatthe molecular sieves contain at least one framework tetrahedral unit inaddition to AlO₂ ⁻ and PO₂ ⁺. "M" is at least one element selected fromthe group consisting of arsenic, beryllium, boron, cobalt, chromium,gallium, qermanium, iron, lithium, magnesium, manganese, titanium andzinc, subject to certain restrictions on the combinations of elements aswill appear from the discussions of individual groups of ELAPOs below.ELAPOs and their preparation are disclosed in European PatentApplication Serial No. 85104386.9, filed Apr. 11, 1985 (EPC PublicationNo. 0158976, published Oct. 13, 1985, incorporated herein by reference)and 85104388.5, filed Apr. 11, 1985 (EPC Publication No. 158349,published Oct. 16, 1985, incorporated herein by reference).

The "ELAPO" molecular sieves further include numerous species which areintended herein to be within the scope of the term "non zeoliticmolecular sieves" such being disclosed in the following copending andcommonly assigned applications, incorporated herein by reference thereto[(A) following a serial number indicates that the application isabandoned, while (CIP) following a serial number indicates that theapplication is a continuation in-part of the immediately precedingapplication, and (C) indicates that the application is a continuation ofthe immediately preceding application]:

    ______________________________________                                        U.S. Ser. No. Filed          NZMS                                             ______________________________________                                        600,166(A)    April 13, 1984 AsAPO                                            830,889(CIP)  Feb. 19, 1986  AsAPO                                            599,812(A)    April 13, 1984 BAPO                                             804,248(C)(A) Dec. 4, 1985   BAPO                                             029,540(CIP)  March 24, 1987 BAPO                                             599,776(A)    April 13, 1984 BeAPO                                            835,293(CIP)  March 3, 1986  BeAPO                                            599,813(A)    April 13, 1984 CAPO                                             830,756(CIP)  Feb. 19, 1986  CAPO                                             599,771(A)    April 13, 1984 GaAPO                                            830,890(CIP)  Feb. 19, 1986  GaAPO                                            599,807(A)    April 13, 1984 GeAPO                                            841,753(CIP)  March 20, 1986 GeAPO                                            599,811(A)    April 13, 1984 LiAPO                                            834,921(CIP)  Feb. 28, 1986  LiAPO                                            600,171       April 13, 1984 FCAPO                                            (now U.S. Pat. No. 4,686,093 issued Auqust 11, 1987)                          600,172(A)    April 13, 1984 ElAPO (M                                                                      comprises                                                                     two                                                                           different                                        846,088(CIP)  March 31, 1986 elements)                                        599,824(A)    April 13, 1984 FeTiAPO                                          902,129(C)    September 2, 1986                                                                            FeTiAPO                                          599,810(A)    April 13, 1984 XAPO                                             902,020(C)    September 2, 1986                                                                            XAPO                                             ______________________________________                                    

The disclosure of the patent listed in the foregoing table isincorporated herein by reference.

The ELAPO molecular sieves are generally referred to herein by theacronym "ELAPO" to designate element(s) "M" in a framework of AlO₂ ⁻,PO₂ ⁺ and MO₂ ^(n) tetrahedral oxide units. Actual class members will beidentified by replacing the "EL" of the acronym with the elementspresent as MO₂ ^(n) tetrahedral units. For example, "MgBeAPO" designatesa molecular sieve comprised of AlO₂ ⁻, PO₂ ⁺, MgO₂ ⁻² and BeO₂ ⁻²tetrahedral units. To identify various structural species which make upeach of the subgeneric classes, each species is assigned a number and isidentified as "ELAPO i" wherein "i" is an integer. The given speciesdesignation is not intended to denote a similarity in structure to anyother species denominated by a similar identification system.

The ELAPO molecular sieves comprise at least one additional elementcapable of forming framework tetrahedral oxide units (MO₂ ^(n)) to formcrystal framework structures with AlO₂ ⁻ and PO₂ ⁺ tetrahedral oxideunits wherein "M" represents at least one element capable of formingtetrahedral units "MO₂ ^(n) " where "n" is -3, -2, -1, 0 or +1 and is atleast one element selected from the group consisting of arsenic,beryllium, boron, cobalt, chromium, gallium, germanium, iron, lithium,magnesium, manganese, titanium and zinc.

The ELAPO molecular sieves have crystalline three-dimensionalmicroporous framework structures of AlO₂ ⁻, PO₂ ⁺ and MO₂ ^(n)tetrahedral units and have an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2 ;

wherein "R" represents at one organic templating agent present in theintracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) PO_(z))O₂ and has a value of zero toabout .0.3; "M" represents at least one element capable of formingframework tetrahedral oxides where "M" is at least one element selectedfrom the group consisting of arsenic, beryllium, boron, cobalt,chromium, gallium, qermanium, iron, lithium, magnesium, manganese,titanium and zinc.

The relative amounts of element(s) "M", aluminum and phosphorous areexpressed by the empirical chemical formula (anhydrous):

    mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2

where "x", "y" and "z" represent the mole fractions of said "M" aluminumand phosphorous. The individual mole fractions of each "M" (or when Mdenotes two or more elements, M₁, M₂, M₃, etc.) may be represented by"x₁ ", "x₂ ", "x₃ ", etc. wherein "x₁ ", "x₂ ", and "x₃ " etc. representthe individual mole fractions of elements M₁, M₂, M₃, and etc. for "M"as above defined. The values of "x₁ ", "x₂ ", "x₃ ", etc. are as definedfor "x", hereinafter, where "x₁ "+"x₂ "+"xhd". . . ="x" and where x₁,x₂, x₃, etc. are each at least 0.01.

The ELAPO molecular sieves have crystalline three-dimensionalmicroporous framework structures of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺tetrahedral units having an empirical chemical composition on ananhydrous basis expressed by the formula:

    mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at one organic templating agent present in theintracrystalline pore system; "m" represents a molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3; "M" represents at least one different element (other than Alor P) capable of forming framework tetrahedral oxides, as hereinbeforedefined, and "x", "y" and "z" represent the mole fractions of "M",aluminum and phosphorous, respectively present as tetrahedral oxides; ingeneral, said mole fractions "x", "y" and "z" are within the followingvalues for "x", "y" and "z", although as will appear hereinbelow, thelimits for "x", "y" and "z" may vary slightly with the nature of theelement "M":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        A       0.02           0.60   0.38                                            B       0.02           0.38   0.60                                            C       0.39           0.01   0.60                                            D       0.98           0.01   0.01                                            E       0.39           0.60   0.01                                            ______________________________________                                    

Also, in general, in a preferred sub-class of the ELAPOs of thisinvention, the values of "x", "y" and "z" in the formula above arewithin the following values for "x", "y" and "z", although again therelevent limits may vary somewhat with the nature of the element "m", asset forth hereinbelow:

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        a       0.02           0.60   0.38                                            b       0.02           0.38   0.60                                            c       0.39           0.01   0.60                                            d       0.60           0.01   0.39                                            e       0.60           0.39   0.01                                            f       0.39           0.60   0.01                                            ______________________________________                                    

ELAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofthe elements "M", aluminum and phosphorus, preferably an organictemplating, i.e., structure-directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between 50° C. and 250° C., and preferablybetween 100° C. and 200° C., until crystals of the ELAPO product areobtained, usually a period of from several hours to several weeks.Typical crystallization times are from about 2 hours to about 30 dayswith from about 2 hours to about 20 days being generally employed toobtain crystals of the ELAPO products. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the ELAPO compositions of the instant invention, it isin general preferred to employ a reaction mixture composition expressedin terms of the molar ratios as follows:

    aR: (M.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and 300; "M" represents at least one element, as abovedescribed, capable of forming tetrahedral oxide framework units, MO₂^(n), with AlO₂ ⁻ and PO₂ ⁺ tetrahedral units; "n" has a value of -3,-2, -1, 0 or +1; and "x", "y" and "z" represent the mole fractions of"M", aluminum and phosphorous, respectively; "y" and "z" each have avalue of at least 0.01 and "x" has a value of at least 0.01 with eachelement "M" having a mole fraction of at least 0.01. In general, themole fractions "x", "y" and "z" are preferably within the followingvalues for "x", "y" and "z":

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        F       0.01           0.60   0.39                                            G       0.01           0.39   0.60                                            H       0.39           0.01   0.60                                            I       0.98           0.01   0.01                                            J       0.39           0.60   0.01                                            ______________________________________                                    

Further guidance concerning the preferred reaction mixtures for formingELAPOs with various elements "M" will be given below.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to a total of (M+Al+P)=(x+y+z)=1.00 mole,whereas in other cases the reaction mixtures are expressed in terms ofmolar oxide ratios and may be normalized to 1.00 mole of P₂ O₅ and/orAl₂ O₃. This latter form is readily converted to the former form byroutine calculations by dividing the total number of moles of "M",aluminum and phosphorous into the moles of each of "M", aluminum andphosphorous. The moles of template and water are similarly normalized bydividing by the total moles of "M", aluminum and phosphorous.

In forming the reaction mixture from which the instant molecular sievesar formed the organic templating agent can be any of those heretoforeproposed for use in the synthesis of conventional zeolitealuminosilicates. In general these compounds contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen,phosphorous, arsenic and antimony, preferably nitrogen or phosphorousand most preferably nitrogen, which compounds also contain at least onealkyl or aryl group having from 1 to 8 carbon atoms. Particularlypreferred compounds for use as templating agents are the amines,quaternary phosphonium compounds and quaternary ammonium compounds, thelatter two being represented generally by the formula R₄ X⁺ wherein "X"is nitrogen or phosphorous and each R is an alkyl or aryl groupcontaining from 1 to 8 carbon atoms. Polymeric quaternary ammonium saltssuch as [(C₁₄ H₃₂ N₂) (OH)₂ ]x wherein "x" has a value of at least 2 arealso suitably employed. The mono-, di- and tri-amines are advantageouslyutilized, either alone or in combination with a quaternary ammoniumcompound or other templating compound. Mixtures of two or moretemplating agents can either produce mixtures of the desired ELAPOs orthe more strongly directing templating species may control the course ofthe reaction with the other templating species serving primarily toestablish the pH conditions of the reaction gel. Representativetemplating agents include tetramethylammonium, tetraethylammonium,tetrapropylammonium or tetrabutylammonium ions; tetrapentylammonium ion;di n propylamine; tripropylamine; triethylamine; triethanolamine;piperidine; cyclohexylamine; 2 methylpyridine; N,N-dimethylbenzylamine;N,N dimethylethanolamine; choline; N,N'-dimethylpiperazine;1,4-diazabicyclo (2,2,2,) octane; N-methyldiethanolamine;N-methylethanolamine; N-methylpiperidine; 3-methylpiperidine;n-methylcyclohexylamine; 3-methylpyridine; 4-methylpyridine;quinuclidine; N,N'-dimethyl 1,4-diazabicyclo (2,2,2) octane ion;di-n-butylamine, neopentylamine; di-n-pentylamine; isopropylamine;t-butylamine; ethylenediamine; pyrrolidine; and 2-imidazolidone. Notevery templating agent will direct the formation of every species ofELAPO, i.e., a single templating agent can, with proper manipulation ofthe reaction conditions, direct the formation of several ELAPOcompositions, and a given ELAPO composition can be produced usingseveral different templating agents. The phosphorous source ispreferably phosphoric acid, but organic phosphates such as triethylphosphate may be satisfactory, and so also may crystalline or amorphousaluminophosphates such as the AlPO₄ composition of U.S. Pat. No.4,310,440. Organophosphorous compounds, such as tetrabutylphosphoniumbromide, do not apparently serve as reactive sources of phosphorous, butthese compounds may function as templating agents. Conventionalphosphorous salts such as sodium metaphosphate, may be used, at least inpart, as the phosphorous source, but are not preferred.

The aluminum source is preferably either an aluminum alkoxide, such asaluminum isopropoxide, or pseudoboehmite. The crystalline or amorphousaluminophosphates which are a suitable source of phosphorous are, ofcourse, also suitable sources of aluminum. Other sources of aluminumused in zeolite synthesis, such as gibbsite, sodium aluminate andaluminum trichloride, can be employed but are not preferred.

The element(s) "M" can be introduced into the reaction system in anyform which permits the formation in situ of reactive form of theelement, i.e., reactive to form the framework tetrahedral oxide unit ofthe element. The organic and inorganic salts, of "M" such as oxides,alkoxides, hydroxides, halides and carboxyates, may be employedincluding the chlorides, bromides, iodides, nitrates, sulfates,phosphates, acetates, formates, and alkoxides, including ethoxides,propoxides and the like. Specific preferred reagents for introducingvarious elements "M" are discussed hereinbelow.

While not essential to the synthesis of ELAPO compositions, stirring orother moderate agitation of the reaction mixture and/or seeding thereaction mixture with seed crystals of either the ELAPO species to beproduced or a topologically similar species, such as aluminophosphate,alumino silicate or molecular sieve compositions, facilitates thecrystallization procedure.

After crystallization the ELAPO product may be isolated andadvantageously washed with water and dried in air. The as synthesizedELAPO generally contains within its internal pore system at least oneform of the templating agent employed in its formation. Most commonlythe organic moiety is present, at least in part, as a charge balancingcation as is generally the case with as-synthesized aluminosilicatezeolites prepared from organic containing reaction systems. It ispossible, however, that some or all of the organic moiety is an occludedmolecular species in a particular ELAPO species. As a general rule thetemplating agent, and hence the occluded organic species, is too largeto move freely through the pore system of the ELAPO product and must beremoved by calcining the ELAPO at temperatures of 200° C. to 700° C. tothermally degrade the organic species. In a few instances the pores ofthe ELAPO product are sufficiently large to permit transport of thetemplating agent, particularly if the latter is a small molecule, andaccordingly complete or partial removal thereof can be accomplished byconventional desorption procedures such as carried out in the case ofzeolites. It will be understood that the term "as synthesized " as usedherein does not include the condition of the ELAPO phase wherein theorganic moiety occupying the intracrystalline pore system as a result ofthe hydrothermal crystallization process has been reduced by postsynthesis treatment such that the value of "m" in the compositionformula:

    mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2

has a value of less than 0.02. The other symbols of the formula are asdefined hereinabove. In those preparations in which an alkoxide isemployed as the source of element "M", aluminum or phosphorous, thecorresponding alcohol is necessarily present in the reaction mixturesince it is a hydrolysis product of the alkoxide. It has not beendetermined whether this alcohol participates in the synthesis process asa templating agent. For the purposes of this application, however, thisalcohol is arbitrarily omitted from the class of templating agents, evenif it is present in the as synthesized ELAPO material.

Since the present ELAPO compositions are formed from MO₂ ^(n), AlO₂ ⁻and PO₂ ⁺ tetrahedral oxide units which, respectively, have a net chargeof "n", (where "n" may be -3, -2, -1, 0 or +1), the matter of cationexchangeability is considerably more complicated than in the case ofzeolitic molecular sieves in which, ideally, there is stoichiometricrelationship between AlO₂ ⁻ tetrahedra and charge-balancing cations. Inthe instant compositions, an AlO₂ ⁻ tetrahedron can be balancedelectrically either by association with a PO₂ ⁺ tetrahedron or a simplecation such as an alkali metal cation, a proton (H⁺), a cation of "M"present in the reaction mixture, or an organic cation derived from thetemplating agent. Similarly, an MO₂ ^(n) tetrahedron, where "n" isnegative, can be balanced electrically by association with PO₂ ⁺tetrahedra, a cation of "M" present in the reaction mixture, organiccations derived from the templating agent, a simple cation such as analkali metal cation, or other divalent or polyvalent metal cation, aproton (H⁺), or anions of cations introduced from an extraneous source.It has also been postulated that non-adjacent AlO₂ ⁻ and PO₂ ⁺tetrahedral pairs can be balanced by Na⁺ and OH⁻ respectively (Flanigenand Grose, Molecular Sieve Zeolites-I, ACS, Washington, D.C. (1971).

AsAPO MOLECULAR SIEVES

The AsAPO molecular sieves of U.S. Ser. No. 600,166, filed Apr. 13,1984, and U.S. Ser. No. 830,889 filed Feb. 19, 1986 have a frameworkstructure of AsO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral units (where "n" is-1 or +1) and have an empirical chemical composition on an anhydrousbasis expressed by the formula

    mR: (As.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (As_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements arsenic, aluminum andphosphorous, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        A       0.01           0.60   0.39                                            B       0.01           0.39   0.60                                            C       0.39           0.01   0.60                                            D       0.60           0.01   0.39                                            E       0.60           0.39   0.01                                            F       0.39           0.60   0.01                                            ______________________________________                                    

There are two preferred subclasses of the AsAPO molecular sieves,depending upon whether the value of "n" is -1 or +1 (i.e. whether thearsenic is trivalent or pentavalent), it being understood that mixturesof such are permitted in a given AsAPO. When "n" is -1, the preferredvalues of x, y and z are within the limiting compositional values orpoints as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        a       0.01           0.59   0.40                                            b       0.01           0.39   0.60                                            c       0.39           0.01   0.60                                            d       0.59           0.01   0.40                                            ______________________________________                                    

When "n" is +1, the preferred values of x, y and z are within thelimiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        e       0.01           0.60   0.39                                            f       0.01           0.40   0.59                                            g       0.59           0.40   0.01                                            h       0.39           0.60   0.01                                            ______________________________________                                    

In an especially preferred subclass of the AsAPO molecular sieves inwhich "n"=+1, the values of x, y and z are as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        i       0.03           0.52   0.45                                            j       0.03           0.45   0.52                                            k       0.08           0.40   0.52                                            l       0.33           0.40   0.27                                            m       0.33           0.41   0.26                                            n       0.22           0.52   0.26                                            ______________________________________                                    

AsAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofarsenic, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such spolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the AsAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, and preferably about 12hours to about 7 days, have been observed. The product is recovered byany convenient method such as centrifugation or filtration.

In synthesizing the AsAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (As.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "x", "y" and "z"represent the mole fractions of arsenic, aluminum and phosphorous,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        G       0.01           0.60   0.39                                            H       0.01           0.39   0.60                                            I       0.39           0.01   0.60                                            J       0.98           0.01   0.01                                            K       0.39           0.60   0.01                                            ______________________________________                                    

Especially preferred reaction mixtures are those wherein the molefractions "x", "y" and "z" are within the limiting compositional valuesor points as follows:

    ______________________________________                                        Mole Fraction                                                                 Point   x              y      z                                               ______________________________________                                        a       0.20           0.55   0.25                                            b       0.20           0.50   0.30                                            c       0.30           0.40   0.30                                            d       0.40           0.40   0.20                                            e       0.40           0.50   0.10                                            f       0.35           0.55   0.10                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieve containing arsenic, aluminum andphosphorus as framework tetrahedral oxide units are prepared as follows:

Preparative Reagents

AsAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare AsAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) As₂ O₅, arsenic (V) oxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures AsAPOs may be prepared by forming a startingreaction mixture by dissolving the arsenic (V) oxide and the H₃ PO₄ inat least part of the water. To this solution the aluminum oxide orisopropoxide is added. This mixture is then blended until a homogeneousmixture is observed. To this mixture the templating agent and theresulting mixture blended until a homogeneous mixture is observed. Themixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure. BAPOMOLECULAR SIEVES

The BAPO molecular sieves of U.S. Ser. No. 599,812, filed Apr. 13, 1984,U.S. Ser. No. 804,248, filed Dec. 4, 1985, and U.S. Ser. No. 029,540,filed March 24, 1987, have a framework structure of BO₂ ⁻, AlO₂ ⁻ andPO₂ ⁺ tetrahedral units and have an empirical chemcial composition on ananhydrous basis expressed by the formula:

    mR: (B.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (B_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, "x", "y" and "z" represent the mole fractions of the elementsboron, aluminum and phosphorus, respectively, present as tetrahedraloxides. The more fractions "x", "y" and "z" are generally defined asbeing within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.39   0.60                                            C        0.39          0.01   0.60                                            D        0.60          0.01   0.39                                            E        0.60          0.39   0.01                                            F        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the BAPO molecular sieves the values of x, y,and z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.01          0.59   0.40                                            b        0.01          0.39   0.60                                            c        0.39          0.01   0.60                                            d        0.59          0.01   0.40                                            ______________________________________                                    

An especially preferred subclass of the BAPO molecular sieves are thosein which the mole fraction, "x", of boron is not greater than about 0.3.

BAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofboron, aluminum and phosphorus, preferably an organic templating, i.e.,structure directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and/or optionally an alkali or other metal .The reaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the BAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 14 days, and preferably about 1 toabout 7 days, have been observed. The product is recovered by anyconvient method such as centrifugation or filtration.

In synthesizing the BAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (B.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

where "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and is an effective amount preferably within therange of greater than zero (0) to about 6, and most preferably not morethan about 1.0; "b" has a value of from zero (0) to about 500,preferably between about 2 and about 300, desirably not greater thanabout 20, and most desirably not greater than about 10; and "x", "y" and"z" represent the mole fractions of boron, aluminum and phosphorus,respectively, and each ha a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        G        0.01          0.60   0.39                                            H        0.01          0.39   0.60                                            I        0.39          0.01   0.60                                            J        0.98          0.01   0.01                                            K        0.39          0.60   0.01                                            ______________________________________                                    

Especially preferred reaction mixtures are those containing from 0.5 to2.0 moles of B₂ O₃ and from 0.75 to 1.25 moles of Al₂ O₃ for each moleof P₂ O₅.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

The exact nature of the BAPO molecular sieves is not entirely understoodat present, although all are believed to contain BO₂, AlO₂ and PO₂tetrahedra in the three dimensional microporous framework structure. Thelow level of boron present in some of the instant molecular sieves makesit difficult to ascertain the exact nature of the interactions amongboron, aluminum and phosphorus. As a result, although it is believedthat BO₂ tetrahedra are present in the three-dimensional microporousframework structure, it is appropriate to characterize certain BAPOcompositions in terms of the molar ratios of oxides. Molecular sievescontaining boron, aluminum and phosphorus as framework tetrahedral oxideunits are prepared as follows:

Preparative Reagents

BAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare BAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) boric acid or trimethylborate;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH:

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinulidine, (C₇ H₁₃ N),

(j) MQuin Methyl Quinuclide hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) c hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures

In the preferred method of synthesizing the BAPO compositions, one firstcombines sources of boron, aluminum and phosphorus to form an amorphousmaterial containing all three elements, and thereafter heats theamorphous material to produce a crystalline BAPO molecular sieve. It isnot necessary that the total quantities of the reactive sources ofboron, aluminum and phosphorus to be used in the final reaction mixturebe present in the amorphous material, since additional quantities of theelements can be added during the later heat treatment; in particular, ithas been found convenient to add additional quantities of phosphorus tothe amorphous material before the heat treatment. The preliminaryformation of the amorphous material assists in the incorporation of theboron into the final molecular sieve.

For example, BAPOs may be prepared by forming a solution of boric acidin a methanolic solution of the templating agent, then adding a hydratedaluminosphosphate and water and stirring to form a homogeneous reactionslurry. This slurry is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

BeAPO MOLECULAR SIEVES

The BeAPO molecular sieves of U.S. Ser. No. 599,776, filed Apr. 13,1984, and U.S. Ser. No. 835,293 filed Mar. 3, 1986 have a frameworkstructure of BeO₂ ⁻², AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Be.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Be_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3 is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements beryllium, aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.39   0.60                                            C        0.39          0.01   0.60                                            D        0.60          0.01   0.39                                            E        0.60          0.39   0.01                                            F        0.39          0.60   0.01                                            ______________________________________                                    

In a preferred subclass of the BeAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.01          0.60   0.39                                            b        0.01          0.39   0.60                                            c        0.35          0.05   0.60                                            d        0.35          0.60   0.05                                            ______________________________________                                    

In an especially preferred subclass of the BeAPO molecular sieves thevalues of x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        e        0.02          0.46   0.52                                            f        0.10          0.38   0.52                                            g        0.10          0.46   0.44                                            ______________________________________                                    

BeAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofberyllium, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the BeAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 14 days, and preferably about 1 toabout 7 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the BeAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Be.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.5; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 50; and "x", "y" and "z"represent the mole fractions of beryllium, aluminum and phosphorus,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        G        0.01          0.60   0.39                                            H        0.01          0.39   0.60                                            I        0.39          0.01   0.60                                            J        0.98          0.01   0.01                                            K        0.39          0.60   0.01                                            ______________________________________                                    

Especially preferred reaction mixtures are those wherein the molefractions "x", "y" and "z" are within the limiting compositional valuesor points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        g        0.04          0.46   0.50                                            h        0.16          0.34   0.50                                            i        0.17          0.34   0.49                                            j        0.17          0.43   0.40                                            k        0.14          0.46   0.40                                            ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing beryllium, aluminum andphosphorus as framework tetrahedral oxide units are prepared as follows:

Preparative Reagents BeAPO compositions may be prepared by usingnumerous reagents. Reagents which may be employed to prepare BeAPOsinclude:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) beryllium sulfate;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclide hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures

BeAPOs may be prepared by forming a starting reaction mixture bydissolving the beryllium sulfate and the H₃ PO₄ in at least part of thewater. To this solution the aluminum oxide or isopropoxide is added.This mixture is then blended until a homogeneous mixture is observed. Tothis mixture the templating agent and the resulting mixture blendeduntil a homogeneous mixture is observed. The mixture is then placed in alined (polytetrafluoroethylene) stainless steel pressure vessel anddigested at a temperature (150° C. or 200° C. for a time or placed inlined screw top bottles for digestion at 100° C. Digestions aretypically carried out under autogenous pressure.

CAPO MOLECULAR SIEVES

The CAPO molecular sieves of U.S. Ser. No. 599,813, filed Apr. 13, 1984,and U.S. Ser. No. 830,756 filed Feb. 19, 1986 have a framework structureof CrO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral units (where "n" is -1, 0 or+1) and have an empirical chemical composition on an anhydrous basisexpressed by the formula

    mR : (Cr.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Cr_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3 is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements chromium, aluminum andphosphorus, respectively, present as tetrahedral oxides. When "n" is -1or +1, the mole fractions "x", "y" and "z" are generally defined asbeing within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.39   0.60                                            C        0.39          0.01   0.60                                            D        0.60          0.01   0.39                                            E        0.60          0.39   0.01                                            F        0.39          0.60   0.01                                            ______________________________________                                    

When "n" is 0, the mole fractions "x", "y" and "z" are generally definedas being within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        G        0.01          0.60   0.39                                            H        0.01          0.47   0.52                                            I        0.94          0.01   0.05                                            J        0.98          0.01   0.01                                            K        0.39          0.60   0.01                                            ______________________________________                                    

There are three preferred subclass of the CAPO molecular sieves,depending upon whether the value of "n" is -1, 0 or +1 (i.e. whether thechromium has an oxidation number of 3, 4 or 5), it being understood thatmixtures of such are permitted in a given CAPO. When "n" is -1, thepreferred values of x, y and z are within the limiting compositionalvalues or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        a        0.01          0.59   0.40                                            b        0.01          0.39   0.60                                            c        0.39          0.01   0.60                                            d        0.59          0.01   0.40                                            ______________________________________                                    

In an especially preferred subclass of these CAPO molecular sieves inwhich "n"=-1, the values of x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        n        0.01          0.52   0.47                                            o        0.01          0.42   0.57                                            p        0.03          0.40   0.57                                            q        0.07          0.40   0.53                                            r        0.07          0.47   0.46                                            s        0.02          0.52   0.46                                            ______________________________________                                    

When "n" is 0, the preferred values of x, y and z are within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        e        0.01          0.60   0.39                                            f        0.01          0.47   0.52                                            g        0.50          0.225  0.275                                           h        0.50          0.40   0.10                                            i        0.30          0.60   0.10                                            ______________________________________                                    

When "n" is +1, the preferred values of x, y and z are within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        j        0.01          0.60   0.39                                            k        0.01          0.40   0.59                                            l        0.59          0.40   0.01                                            m        0.39          0.60   0.10                                            ______________________________________                                    

Since the exact nature of the CAPO molecular sieves is not clearlyunderstood at present, although all are believed to contain CrO₂tetrahedra in the three dimensional microporous crystal frameworkstructure, it is advantageous to characterize the CAPO molecular sievesby means of their chemical composition. This is due to the low level ofchromium present in certain of the CAPO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between chromium, aluminum and phosphorous. As a result,although it is believed that CrO₂ tetrahedra are substitutedisomorphously for AlO₂ or PO₂ tetrahedra, it is appropriate tocharacterize certain CAPO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

CAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofchromium, aluminum and phosphorous, preferably an organic templating,i.e., structure directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the CAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, and preferably about 1 toabout 10 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the CAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Cr.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.6; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20; and "x", "y" and "z"represent the mole fractions of chromium, aluminum and phosphorous,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        L        0.01           0.60   0.39                                           M        0.01           0.39   0.60                                           N        0.39           0.01   0.60                                           O        0.98           0.01   0.01                                           P        0.39           0.60   0.01                                           ______________________________________                                    

Especially preferred reaction mixtures are those containing from about0.1 to about 0.4 moles of chromium, and from about 0.75 to about 1.25moles of aluminum, per mole of phosphorous.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing chromium, aluminum andphosphorous as framework tetrahedral oxide units are prepared asfollows:

Preparative Reagents

CAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare CAPOs include:

(a) aluminum isopropoxide, or aluminum chlorhydrol;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) chromium (III) orthophosphate, chromium (III) acetate and chromiumacetate hydroxide, (Cr₃ (OH)₂ (CH₃ COO)₇);

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide:

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures

CAPOs may be prepared by forming a starting reaction mixture by addingaluminum chlorhydrol or aluminum oxide to a solution of chromium acetatehydroxide in water, then adding successively phosphoric acid and thetemplating agent. Between each addition, and after formation of thefinal mixture, the mixture is blended until a homogeneous mixture isobserved.

Alternatively, the phosphoric acid may be mixed with at least part ofthe water, and aluminum oxide or isopropoxide mixed in. A solution ofchromium acetate hydroxide is then added, followed by the templatingagent, and the resultant mixture mixed until homogeneous.

In a third procedure, amorphous chromium phosphate is ground dry withaluminum oxide and the resultant dry mixture added to an aqueoussolution of phosphoric acid in an ice bath. The templating agent is thenadded, and the final mixture mixed until homogenous.

Whichever technique is employed to produce the reaction mixture, thismixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure

GaAPO MOLECULAR SIEVES

The GaAPO molecular sieves of U.S. Ser. No. 599,771, filed Apr. 13,1984, and U.S. Ser. No. 830,890 filed Feb. 19, 1986 have a frameworkstructure of GaO₂ ⁻, AlO₂ and PO₂ ⁺ tetrahedral units and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Ga.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ga_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements gallium, aluminum andphosphorous, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.34   0.65                                           C        0.34           0.01   0.65                                           D        0.60           0.01   0.39                                           E        0.60           0.39   0.01                                           F        0.39           0.60   0.01                                           ______________________________________                                    

In general, the value of "z" in the GaAPO molecular sieves is notgreater than about 0.60.

In a preferred subclass of the GaAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.59   0.40                                           b        0.01           0.34   0.65                                           c        0.34           0.01   0.65                                           d        0.59           0.01   0.40                                           ______________________________________                                    

In an especially preferred subclass of the GaAPO molecular sieve thevalues of x, y and z are as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        e        0.03           0.52   0.45                                           f        0.03           0.33   0.64                                           g        0.16           0.20   0.64                                           h        0.25           0.20   0.55                                           i        0.25           0.33   0.42                                           j        0.06           0.52   0.42                                           ______________________________________                                    

GaAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgallium, aluminum and phosphorus, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C., until crystals of the GaAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 4 hours to about 20 days, and preferably about 1 toabout 7 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the GaAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Ga.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 1.0; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably between about 2 and 20; and "x", "y" and "z" representthe mole fractions of gallium, aluminum and phosphorous, respectively,and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        G        0.01           0.60   0.39                                           H        0.01           0.39   0.60                                           I        0.39           0.01   0.60                                           J        0.98           0.01   0.01                                           K        0.39           0.60   0.01                                           ______________________________________                                    

Especially preferred reaction mixtures are those containing from 0.2 to0.5 mole of Ga₂ O₃ and from 0.3 to 1 mole of Al₂ O₃ for each mole of P₂O₅.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing gallium, aluminum andphosphorous as framework tetrahedral oxide units are prepared asfollows:

Preparative Reagents

GaAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GaAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid:

(d) gallium sulfate or gallium (III) hydroxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures

GaAPOs may be prepared by forming a starting reaction mixture by mixingthe phosphoric acid with at least part of the water. To this solutionthe aluminum oxide or isopropoxide is added. This mixture is thenblended until a homogenous mixture is observed. To this mixture thegallium sulfate or gallium hydroxide and the templating agent aresuccessively added and the resulting mixture blended until a homogeneousmixture is observed.

Alternatively, the aluminum oxide may be mixed with a solution of thegallium sulfate or hydroxide, and then the phosphoric acid and thetemplating agent successively added. The resulting mixture is thenblended until a homogeneous mixture is observed.

In a third process, the templating agent may be dissolved in water, thegallium hydroxide or sulfate added with stirring, a solution of thephosphoric acid added, and finally the aluminum oxide mixed in. Theresulting mixture is then blended until a homogeneous mixture isobserved.

Whichever technique is employed to form the reaction mixture, themixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressures.

GeAPO MOLECULAR SIEVES

The GeAPO molecular sieves of U.S. Ser. No. 599,807, filed Apr. 13,1984, and U.S. Ser. No. 841,753 filed Mar. 20, 1986 have a frameworkstructure of GeO₂, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Ge.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Ge_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.2; and "x", "y" and "z"represent the mole fractions of the elements germanium, aluminum andphosphorus, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.47   0.52                                           C        0.94           0.01   0.05                                           D        0.98           0.01   0.01                                           E        0.39           0.60   0.01                                           ______________________________________                                    

In a preferred subclass of the GeAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.60   0.39                                           b        0.01           0.47   0.52                                           c        0.50           0.225  0.275                                          d        0.50           0.40   0.10                                           e        0.30           0.60   0.10                                           ______________________________________                                    

An especially preferred subclass of the GeAPO molecular sieves are thosein which the value of "x" is not greater than about 0.13.

GeAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofgermanium, aluminum and phosphorous, preferably an organic templating,i.e., structure directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C., until crystals of the GeAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, and preferably about 1 toabout 10 days, have been observed. The product is recovered by anyconvenient method such as centrifugation or filtration.

In synthesizing the GeAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Ge.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 0.6; "b" has a valueof from zero (0) to about 500, preferably between about 2 and about 300,most preferably between about 10 and about 60; and "x" , "y" and "z"represent the mole fractions of germanium, aluminum and phosphorous,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        F        0.01           0.60   0.39                                           G        0.01           0.39   0.60                                           H        0.39           0.01   0.60                                           I        0.98           0.01   0.01                                           J        0.39           0.60   0.01                                           ______________________________________                                    

Especially preferred reaction mixtures are those containing from 0.2 to0.4 mole of GeO₂ and from 0.75 to 1.25 mole of Al₂ O₃ for each mole ofP₂ O₅.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole. Molecular sieves containing germanium, aluminum andphosphorous as framework tetrahedral oxide units are prepared asfollows:

Preparative Reagents

GeAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare GeAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) germanium tetrachloride, germanium ethoxide and germanium dioxide;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures

In some cases, it may be advantageous, when synthesizing the GeAPOcompositions, to first combine sources of germanium and aluminum, toform a mixed germanium/aluminum compound (this compound being typicallya mixed oxide) and thereafter to combine this mixed compound with asource of phosphorous to form the final GeAPO composition. Such mixedoxides may be prepared for example by hydrolyzing aqueous solutionscontaining germanium tetrachloride and aluminum chlorhydrol, or aluminumtri-sec-butoxide.

GeAPOs may be prepared by forming a starting reaction mixture by mixingthe phosphoric acid with at least part of the water. To this solution isadded the mixed qermanium/aluminum oxide prepared as described above.This mixture is then blended until a homogeneous mixture is observed. Tothis mixture the templating agent is added and the resulting mixtureblended until a homogeneous mixture is observed.

Alternatively, to a solution of aluminum isopropoxide may be addedgermanium ethoxide. The resultant solution may optionally be dried toproduce a mixed oxide. To the mixed solution or dried oxide are addedsuccessively the phosphoric acid and the templating agent. The resultingmixture is then blended until a homogeneous mixture is observed.

In a third process, a solution is formed by dissolving the phosphoricacid in water, adding aluminum oxide or isopropoxide and mixingthoroughly. To the resultant mixture is added a solution containing thetemplating agent and germanium dioxide. The resulting mixture is thenblended until a homogeneous mixture is observed.

Whichever technique is employed to form the reaction mixture, themixture is then placed in a lined (polytetrafluoroethylene) stainlesssteel pressure vessel and digested at a temperature (150° C. or 200° C.)for a time or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure.

LiAPO MOLECULAR SIEVES

The LiAPO molecular sieves of U.S. Ser. No. 599,811, filed Apr. 13,1984, and U.S. Ser. No. 834,921 filed Feb, 28, 1986 have a frameworkstructure of LiO₂ ⁻³, AlO₂ ⁻ and PO₂ ⁺ tetrahedral units and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (Li.sub.x Al.sub.y P.sub.2)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Li_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3 is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements lithium, aluminum andphosphorous, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.01           0.60   0.39                                           B        0.01           0.39   0.60                                           C        0.39           0.01   0.60                                           D        0.60           0.01   0.39                                           E        0.60           0.39   0.01                                           F        0.39           0.60   0.01                                           ______________________________________                                    

In a preferred subclass of the LiAPO molecular sieves the values of x, yand z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.01           0.60   0.39                                           b        0.01           0.39   0.60                                           c        0.35           0.05   0.60                                           d        0.35           0.60   0.05                                           ______________________________________                                    

In an especially preferred subclass of the LiAPO molecular sieves thevalues of x, y and z are within the following limits:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        e        0.01           0.52   0.47                                           f        0.01           0.47   0.52                                           g        0.03           0.45   0.52                                           h        0.10           0.45   0.45                                           i        0.10           0.49   0.41                                           j        0.07           0.52   0.41                                           ______________________________________                                    

LiAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources oflithium, aluminum and phosphorous, preferably an organic templating,i.e., structure-directing, agent, preferably a compound of an element ofGroup VA of the Periodic Table, and/or optionally an alkali or othermetal. The reaction mixture is generally placed in a sealed pressurevessel, preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the LiAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 12 hours to about 5 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the LiAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (Li.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than about 2; "b" has a valueof from zero (0) to about 500, preferably between 2 and 300, mostpreferably not greater than about 40; and "x", "y" and "z" represent themole fractions of lithium, aluminum and phosphorous, respectively, andeach has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        G        0.01           0.60   0.39                                           H        0.01           0.39   0.60                                           I        0.39           0.01   0.60                                           J        0.98           0.01   0.01                                           K        0.39           0.60   0.01                                           ______________________________________                                    

In an especially preferred subclass of the reaction mixtures, the valuesof "x", "y" and "z" are within the limiting compositional values orpoints as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        l        0.03           0.50   0.47                                           m        0.03           0.45   0.52                                           n        0.08           0.40   0.52                                           o        0.10           0.40   0.50                                           q        0.04           0.50   0.46                                           ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

Since the exact nature of the LiAPO molecular sieves is not clearlyunderstood at present, although all are believed to contain LiO₂tetrahedra in the three dimensional microporous crystal frameworkstructure, it is advantageous to characterize the LiAPO molecular sievesby means of their chemical composition. This is due to the low level oflithium present in certain of the LiAPO molecular sieves prepared todate which makes it difficult to ascertain the exact nature of theinteraction between lithium, aluminum and phosphorous. As a result,although it is believed that LiO₂ tetrahedra are substitutedisomorphously for AlO₂ or PO₂ tetrahedra, it is appropriate tocharacterize certain LiAPO compositions by reference to their chemicalcomposition in terms of the mole ratios of oxides.

Molecular sieves containing lithium, aluminum and phosphorous asframework tetrahedral oxide units are prepared as followed:

Preparative Reagents

LiAPO compositions may be prepared by using numerous reagents. Reagentswhich may be employed to prepare LiAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) lithium sulfate or lithium orthophosphate;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures

LiAPOs may be prepared by forming a starting reaction mixture bysuspending aluminum oxide in at least part of the water. To this mixturethe templating agent is added. The resultant mixture is then blendeduntil a homogeneous mixture is observed. To this mixture the lithiumphosphate or sulfate is added and the resulting mixture blended until ahomogeneous mixture is observed. Alternatively, an initial mixture maybe formed by mixing aluminum oxide and lithium phosphate or sulfate. Tothe resultant mixture are added successively phosphoric acid and anaqueous solution of the templating agent, and the resulting mixtureblended until a homogeneous mixture is observed.

In a third procedure, the phosphoric acid is mixed with at least part ofthe water, and the aluminum oxide is mixed in. To the resultant mixtureare added lithium sulfate and the templating agent, and the resultingmixture blended until a homogeneous mixture is observed.

Whichever procedure is adopted to form the reaction mixture, the mixtureis then placed in a lined (polytetrafluoroethylene) stainless steelpressure vessel and digested at a temperature (150° C. or 200° C.) for atime or placed in lined screw top bottles for digestion at 100° C.Digestions are typically carried out under autogenous pressure

FeTiAPO MOLECULAR SIEVES

The FeTiAPO molecular sieves of U.S. Ser. No. 599,824, filed Apr. 13,1984, and U.S. Ser. No. 902,129 filed Sept. 2, 1986 have threedimensional microporous framework structures of FeO₂ ^(n), TiO₂, AlO₂ ⁻and PO₂ ⁺ tetrahedral oxide units, where "n" is -2 or -1, and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR: (M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents iron and titanium; "m"represents the molar amount of "R" present per mole of (M_(x) Al_(y)P_(z))O₂ and has a value of zero (0) to about 0.3; and "x", "y" and "z"represent the mole fractions of "M", aluminum and phosphorus,respectively present as tetrahedral oxides. The mole fractions "x", "y"and "z" are generally defined as being within the limiting compositionalvalues or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.02           0.60   0.38                                           B        0.02           0.38   0.60                                           C        0.39           0.01   0.60                                           D        0.98           0.01   0.01                                           E        0.39           0.60   0.01                                           ______________________________________                                    

In a preferred subclass of the FeTiAPO molecular sieves the values of x,y and z are within the limiting compositional values or points asfollows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.02           0.60   0.38                                           b        0.02           0.38   0.60                                           c        0.39           0.01   0.60                                           d        0.60           0.01   0.39                                           e        0.60           0.39   0.01                                           f        0.39           0.60   0.01                                           ______________________________________                                    

FeTiAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources ofiron, titanium, aluminum and phosphorous, preferably an organictemplating, i.e., structure directing, agent, preferably a compound ofan element of Group VA of the Periodic Table, and/or optionally analkali or other metal. The reaction mixture is generally placed in asealed pressure vessel, preferably lined with an inert plastic materialsuch as polytetrafluoroethylene and heated, preferably under autogenouspressure at a temperature between about 50° C. and about 250° C., andpreferably between about 100° C. and about 200° C. until crystals of theFeTiAPO product are obtained, usually a period of from several hours toseveral weeks. Typical effective times of from 2 hours to about 30 days,generally from about 12 hours to about 5 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the FeTiAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR: (M.sub.x Al.sub.y P.sub.z)O.sub.2 : bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "b" has a value of from zero (0) to about 500, preferablybetween about 2 and about 300; and "x", "y" and "z" represent the molefractions of "M" (iron and titanium), aluminum and phosphorous,respectively, and each has a value of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        F        0.02           0.60   0.38                                           G        0.02           0.38   0.60                                           H        0.39           0.01   0.60                                           I        0.98           0.01   0.01                                           J        0.39           0.60   0.01                                           ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

Molecular sieves containing iron, titanium, aluminum and phosphorous asframework tetrahedral oxide units are prepared as follows:

Preparative Reagents

FeTiAPO compositions may be prepared by numerous reagents. The preferredsources of iron and titanium for preparing FeTiAPOs are the same asthose for preparing the FeAPOs and TiAPOs already described above. Otherreagents which may be employed to prepare FeTiAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(e) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(f) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(g) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(h) Quin: Quinuclidine, (C₇ H₁₃ N);

(i) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(j) C-hex: cyclohexylamine;

(k) TMAOH: tetramethylammonium hydroxide;

(l) TPAOH: tetrapropylammonium hydroxide; and

(m) DEEA: 2-diethylaminoethanol.

Preparative Procedures

FeTiAPOs may be prepared by forming a homogeneous reaction mixturecontaining reactive sources of iron, titanium, aluminum and phosphorous.The reaction mixture is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

XAPO MOLECULAR SIEVES

The XAPO molecular sieves of U.S. Ser. No. 599,810, filed Apr. 13, 1984,and U.S. Ser. No. 902,020 filed September 2, 1986 have a threedimensional microporous framework structure of MO₂ ^(n), AlO₂ ⁻ and PO₂⁺ tetrahedral oxide units, where "n" is 0, -1 or -2, and have anempirical chemical composition on an anhydrous basis expressed by theformula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "M" represents at least one elementfrom each of the classes of: (1) iron and titanium; and (2) cobalt,magnesium, manganese and zinc; "n" is 0, -1 or -2; "m" represents amolar amount of "R" present per mole of (M_(x) Al_(y) P_(z))O₂ and has avalue of zero (0) to about 0.3; and "x", "y" and "z" represent the molefractions of "M", aluminum and phosphorus, respectively, present astetrahedral oxides. The mole fractions "x", "y" and "z" are generallydefined as being within the limiting compositional values or points asfollows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.02           0.60   0.38                                           B        0.02           0.38   0.60                                           C        0.39           0.01   0.60                                           D        0.98           0.01   0.01                                           E        0.39           0.60   0.01                                           ______________________________________                                    

In a preferred subclass of the XAPO molecular sieves the values of x, y,and z are within the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.02           0.60   0.38                                           b        0.02           0.38   0.60                                           c        0.39           0.01   0.60                                           d        0.60           0.01   0.39                                           e        0.60           0.39   0.01                                           f        0.39           0.60   0.01                                           ______________________________________                                    

XAPO compositions are generally synthesized by hydrothermalcrystallization from a reaction mixture containing reactive sources of"M", aluminum and phosphorous, preferably an organic templating, i.e.,structure-directing, agent, preferably a compound of an element of GroupVA of the Periodic Table, and/or optionally an alkali or other metal.The reaction mixture is generally placed in a sealed pressure vessel,preferably lined with an inert plastic material such aspolytetrafluoroethylene and heated, preferably under autogenous pressureat a temperature between about 50° C. and about 250° C., and preferablybetween about 100° C. and about 200° C. until crystals of the XAPOproduct are obtained, usually a period of from several hours to severalweeks. Typical effective times of from 2 hours to about 30 days,generally from about 2 hours to about 20 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the XAPO compositions, it is preferred to employ areaction mixture composition expressed in terms of the molar ratios asfollows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6; "M" represents at least one element from each of the classesof: (1) iron and titanium; and 2) cobalt, magnesium, manganese and zinc;"b" has a value of from zero (0) to about 500, preferably between about2 and about 300; and "x", "y" and "z" represent the mole fractions of"M" (iron and/or titanium, and at least one of cobalt, magnesium,manganese and zinc), aluminum and phosphorous, respectively, and eachhas a value of at least 0 01, with the proviso that "x" has a value ofat least 0.02.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        F        0.02           0.60   0.38                                           G        0.02           0.38   0.60                                           H        0.39           0.01   0.60                                           I        0.98           0.01   0.01                                           J        0.39           0.60   0.01                                           ______________________________________                                    

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

XAPO molecular sieves are prepared as follows:

Preparative Reagents

XAPO compositions may be prepared by using numerous reagents. Thepreferred sources of elements "M" for preparing XAPOs are the same asthose for preparing other APOs containing the same elements, asdescribed above and below. Other reagents which may be employed toprepare XAPOs include:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(e) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(f) Pr₂ NH: di-n-propylamine, (C₃ H₇)₂ NH;

(g) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N

(h) Quin: Quinuclidine, (C₇ H₁₃ N);

(i) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(j) C-hex: cyclohexylamine;

(k) TMAOH: tetramethylammonium hydroxide

(l) TPAOH: tetrapropylammonium hydroxide; and

(m) DEEA: 2-diethylaminoethanol.

Preparative Procedures

XAPOs may be prepared by forming a homogenous reaction mixturecontaining reactive sources of element "M", aluminum and phosphorous.The reaction mixture is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

MIXED-ELEMENT APO MOLECULAR SIEVES

The mixed element APO molecular sieves of U.S. Ser. No. 599,978, filedApr. 13, 1984, and U.S. Ser. No. 846,088 filed Mar. 31, 1986 have aframework structure of MO₂ ^(n), AlO₂ ⁻ and PO₂ ⁺ tetrahedral units,wherein MO₂ ^(n) represents at least two different elements present astetrahedral units "MO₂ ^(n) " with charge "n", where "n" may be -3, -2,-1, or 0 or +1. One of the elements "M" is selected from the groupconsisting of arsenic, beryllium, boron, chromium, gallium, qermanium,lithium and vanadium, while a second one of the elements "M" is selectedfrom the group consisting of cobalt, iron, magnesium, manganese,titanium and zinc. Preferably, "M" is a mixture of lithium andmagnesium. The mixed element molecular sieves have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of zero toabout 0.3, but is preferably not greater than 0.15; and "x", "y" and "z"represent the mole fractions of the elements "M" i.e. "x" is the totalof the mole fractions of the two or more elements "M"), aluminum andphosphorous, respectively, present as tetrahedral oxides. The molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        A        0.02           0.60   0.38                                           B        0.02           0.38   0.60                                           C        0.39           0.01   0.60                                           D        0.98           0.01   0.01                                           E        0.39           0.60   0.01                                           ______________________________________                                    

In a preferred subclass of the mixed-element APO molecular sieves thevalues of x, y and z are within the limiting compositional values orpoints as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        a        0.02           0.60   0.38                                           b        0.02           0.38   0.60                                           c        0.39           0.01   0.60                                           d        0.60           0.01   0.39                                           e        0.60           0.39   0.01                                           f        0.39           0.60   0.01                                           ______________________________________                                    

An especially preferred subclass of the mixed-element APO molecularsieves are those in which the value of x is not greater than about 0.10.

A second group (FCAPO's) of mixed element PO molecular sieves aredescribed in U.S. Pat. No. 4,686,093 issued Aug. 11, 1987 (incorporatedherein by reference).

The mixed-element APO compositions are generally synthesized byhydrothermal crystallization from a reaction mixture containing reactivesources of the elements "M", aluminum and phosphorous, preferably anorganic templating, i.e., structure-directing, agent, preferably acompound of an element of Group VA of the Periodic Table, and/oroptionally an alkali or other metal. The reaction mixture is generallyplaced in a sealed pressure vessel, preferably lined with an inertplastic material such as polytetrafluoroethylene and heated, preferablyunder autogenous pressure at a temperature between about 50° C. andabout 250° C., and preferably between about 100° C. and about 200° C.until crystals of the APO product are obtained, usually a period of fromseveral hours to several weeks. Typical effective times of from 2 hoursto about 30 days, generally from about 2 hours to about 20 days, andpreferably about 12 hours to about 5 days, have been observed. Theproduct is recovered by any convenient method such as centrifugation orfiltration.

In synthesizing the mixed element APO compositions, it is preferred toemploy a reaction mixture composition expressed in terms of the molarratios as follows:

    aR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 :bH.sub.2 O

wherein "R" is an organic templating agent; "a" is the amount of organictemplating agent "R" and has a value of from zero to about 6 and ispreferably an effective amount within the range of greater than zero (0)to about 6, and most preferably not more than 0.5; "b" has a value offrom zero (0) to about 500, preferably between about 2 and about 300,most preferably not greater than about 20, and most desirably not morethan about 10; and "x", "y" and "z" represent the mole fractions of "M",aluminum and phosphorous, respectively, "y" and "z" each having a valueof at least 0.01 and "x" having a value of at least 0.02, with eachelement "M" having a mole fraction of at least 0.01.

In one embodiment the reaction mixture is selected such that the molefractions "x", "y" and "z" are generally defined as being within thelimiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x              y      z                                              ______________________________________                                        F        0.02           0.60   0.38                                           G        0.02           0.38   0.60                                           H        0.39           0.01   0.60                                           I        0.98           0.01   0.01                                           J        0.39           0.60   0.01                                           ______________________________________                                    

Preferred reaction mixtures are those containing not more than about 0.2moles of the metals "M" per mole of phosphorous.

In the foregoing expression of the reaction composition, the reactantsare normalized with respect to the total of "x", "y" and "z" such that(x+y+z)=1.00 mole.

Since the exact nature of the mixed element APO molecular sieves is notclearly understood at present, although all are believed to contain MO₂tetrahedra in the three dimensional microporous crystal frameworkstructure, it is advantageous to characterize the mixed element APOmolecular sieves by means of their chemical composition. This is due tothe low level of the elements "M" present in certain of themixed-element APO molecular sieves prepared to date which makes itdifficult to ascertain the exact nature of the interaction between themetals "M", aluminum and phosphorous. As a result, although it isbelieved that MO₂ tetrahedra are substituted isomorphously for AlO₂ orPO₂ tetrahedra, it is appropriate to characterize certain mixed-elementAPO compositions by reference to their chemical composition in terms ofthe mole ratios of oxides.

Molecular sieves containing the metals "M", aluminum and phosphorous asframework tetrahedral oxide units are prepared as follows:

Preparative Reagents

Mixed-element APO compositions may be prepared by using numerousreagents. Reagents which may be employed to prepare mixed element APOsinclude:

(a) aluminum isopropoxide;

(b) pseudoboehmite or other aluminum oxide;

(c) H₃ PO₄ : 85 weight percent aqueous phosphoric acid;

(d) lithium phosphate or magnesium hydroxide or appropriate salts of theother elements "M", as described above;

(e) TEAOH: 40 weight percent aqueous solution of tetraethylammoniumhydroxide;

(f) TBAOH: 40 weight percent aqueous solution of tetrabutylammoniumhydroxide;

(g) Pr₂ NH di-n-propylamine, (C₃ H₇)₂ NH;

(h) Pr₃ N: tri-n-propylamine, (C₃ H₇)₃ N;

(i) Quin: Quinuclidine, (C₇ H₁₃ N);

(j) MQuin: Methyl Quinuclidine hydroxide, (C₇ H₁₃ NCH₃ OH);

(k) C-hex: cyclohexylamine;

(l) TMAOH: tetramethylammonium hydroxide;

(m) TPAOH: tetrapropylammonium hydroxide; and

(n) DEEA: 2-diethylaminoethanol.

Preparative Procedures

Mixed element APOs may be prepared by forming a starting reactionmixture by mixing aluminum oxide, magnesium hydroxide, lithium phosphate(or the corresponding salts of the other elements "M"). To this mixturethe phosphoric acid is added. The resultant mixture is then blendeduntil a homogeneous mixture is observed. To this mixture the templatingagent is added and the resulting mixture blended until a homogeneousmixture is observed.

The reaction mixture is then placed in a lined (polytetrafluoroethylene)stainless steel pressure vessel and digested at a temperature (150° C.or 200° C.) for a time or placed in lined screw top bottles fordigestion at 100° C. Digestions are typically carried out underautogenous pressure.

SILICOALUMINOPHOSPHATE MOLECULAR SIEVES

The preferred NZMSs, to date, are the silicoaluminophosphate molecularsieves described in U.S. Pat. No. 4,440,871 (incorporated herein byreference), and U.S. Ser. No. 575,745, filed Jan. 31, 1984.

Medium pore (MP)-SAPOs include SAPO-11, SAPO-31, SAPO-40 and SAPO-41.

The species SAPO-11 has a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-11                                                                                                 Relative                                            2θ         d(Å) Intensity                                           ______________________________________                                         9.4-9.65        9.41-9.17                                                                              m                                                   20.3-20.6        4.37-4.31                                                                              m                                                   21.0-21.3        4.23-4.17                                                                              vs                                                  21.1-22.35       4.02-3.99                                                                              m                                                   22.5-22.9(doublet)                                                                             3.95-3.92                                                                              m                                                   23.15-23.35      3.84-3.81                                                                              m-s                                                 ______________________________________                                    

The species SAPO-31 has a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-31                                                                                                Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        8.5-8.6        10.40-10.28                                                                             m- s                                                 20.2-20.3      4.40-4.37 m                                                    21.9-22.1      4.06-4.02 w- m                                                 22.6-22.7      3.93-3.92 vs                                                   31.7-31.8      2.823-2.814                                                                             w- m                                                 ______________________________________                                    

The species SAPO-40 has a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-40                                                                                                Relative                                             2Θ       d(Å)  Intensity                                            ______________________________________                                        7.5-7.7        11.79-11.48                                                                             vw- m                                                8.0-8.1        11.05-10.94                                                                             s- vs                                                12.4-12.5      7.14-7.08 w- vs                                                13.6-13.8      6.51-6.42 m- s                                                 14.0-14.1      6.33-6.28 w- m                                                 27.8-28.0      3.209-3.18                                                                              w- m                                                 ______________________________________                                    

The species SAFO-41 has a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-41                                                                                                Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        13.6-13.8      6.51-6.42 w- m                                                 20.5-20.6      4.33-4.31 w- m                                                 21.1-21.3      4.21-4.17 vs                                                   22.1-22.3      4.02-3.99 m- s                                                 22.8-23.0      3.90-3.86 m                                                    23.1-23.4      3.82-3.80 w- m                                                 25.5-25.9      3.493-3.44                                                                              w- m                                                 ______________________________________                                    

Large pore(LP)-SAPOs include SAPO-5 and SAPO-37.

The species SAPO-5 has a characteristic X-ray powder diffraction patternwhich contains at least the d-spacing set forth below:

    ______________________________________                                        SAPO-5                                                                                                 Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        13.6-13.8      6.51-6.42 w- m                                                 7.35-7.65      11.79-11.48                                                                             vw- m                                                 19.6-19.95    11.05-10.94                                                                             s- vs                                                20.9-21.3      7.14-7.08 w- vs                                                22.3-22.6      6.51-6.42 m- s                                                 25.85-26.15    3.46-3.40 w- m                                                 27.8-28.0      3.209-3.18                                                                              w- m                                                 ______________________________________                                    

The species SAPO-37 has a characteristic X-ray powder diffractionpattern which contains at least the d-spacings set forth below:

    ______________________________________                                        SAPO-37                                                                                                Relative                                             2θ       d(Å)  Intensity                                            ______________________________________                                        13.6-13.8      6.51-6.42 w- m                                                 6.1-6.3        14.49-14.03                                                                             vs                                                   15.5-15.7      5.72-5.64 w- m                                                 18.5-18.8      4.80-4.72 w- m                                                 23.5-23.7      3.79-3.75 w- m                                                 26.9-27.1      3.31-3.29 w- m                                                 ______________________________________                                    

The NZMSs which may be employed in the instant invention can becharacterized in their calcined form by an adsorption of isobutane of atleast 2 percent by weight, preferably at least 4 percent by weight, at apartial pressure of 500 torr and a temperature of 20° C. The nonzeolitic molecular sieves are also desirably characterized by anadsorption of triethylamine of from zero to less than 5 percent byweight, preferably less than 3 weight percent, at a partial pressure of2.6 torr and a temperature of 22° C. NZMSs characterized by the abovedescribed adsorption of isobutane include, but are not limited to,ELAPSO-5, ELAPSO-11, ELAPSO-31, ELAPSO-36, ELAPSO-37, ELAPSO-40,ELAPSO-41, SAPO-5, SAPO-11, SAPO-31, SAPO-36, SAPO-37, SAPO-40, SAPO-41,CoAPSO-5, CoAPSO-11, CoAPSO-31, CoAPSO-36, CoAPSO-37, CoAPSO-40,CoAPSO-41, FeAPSO-5, FeAPSO-11, FeAPSO-31, FeAPSO-36, FeAPSO-37,FeAPSO-40, FeAPSO-41, MgAPSO-5, MgAPSO-11, MgAPSO-31, MgAPSO-36,MgAPSO-37, MgAPSO-40, MgAPSO-41, MnAPSO-5, MnAPSO-11, MnAPSO-31,MnAPSO-36, MnAPSO-37, MnAPSO-40, MnAPSO-41, TiAPSO-5, TiAPSO-11,TiAPSO-31, TiAPSO-36, TiAPSO-37, TiAPSO-40, TiAPSO-41, ZnAPSO-5,ZnAPSO-11, ZnAPSO-31, ZnAPSO-36, ZnAPSO-37, ZnAPSO-40, ZnAPSO-41,CoMnAPSO-5, CoMnAPSO-11, CoMnAPSO-36, CoMnAPSO-37, CoMnAPSO-40,CoMnAPSO-41, CoMnMgAPSO-5, CoMnMgAPSO-11, CoMnMgAPSO-31, CoMnMgAPSO-36,CoMnMgAPSO-37, CoMnMgAPSO-40, CoMnMgAPSO-41, AsAPSO-5, AsAPSO-11,AsAPSO-31, AsAPSO-36, AsAPSO-37, AsAPSO-40, AsAPSO-41, BAPSO-5,BAPSO-11, BAPSO-31, BAPSO-36, BAPSO-37, BAPSO-40, BAPSO-41, BeAPSO-5,BeAPSO-11, BeAPSO-31, BeAPSO-36, BeAPSO-37, BeAPSO-40, BeAPSO-41,CAPSO-5, CAPSO-11, CAPSO-31, CAPSO-36, CAPSO-37, CAPSO-40, CAPSO-41,GaAPSO-5, GaAPSO-11, GaAPSO-31, GaAPSO-36, GaAPSO-37, GaAPSO-40,GaAPSO-41, GeAPSO-5, GeAPSO-11, GeAPSO-31, GeAPSO-36, GeAPSO-37,GeAPSO-40, GeAPSO-41, LiAPSO-5, LiAPSO-11, LiAPSO-31, LiAPSO-36,LiAPSO-37, LiAPSO-40, LiAPSO-41, MeAPO-5, MeAPO-11, MeAPO-31, MeAPO-36,MeAPO-37, MeAPO-40, MeAPO-41, TiAPO-5, TiAPO-11, TiAPO-31, TiAPO-36,TiAPO-37, TiAPO-40, TiAPO-41, FCAPO-5, FCAPO-11, FCAPO-31, FCAPO-36,FCAPO-37, FCAPO-40, FCAPO-41, AsAPO-5, AsAPO-11, AsAPO-31, AsAPO-36,AsAPO-37, AsAPO-40, AsAPO-41, BAPO-5, BAPO-11, BAPO-31, BAPO-36,BAPO-37, BAPO-40, BAPO-41, BeAPO-5, BeAPO-11, BeAPO-31, BeAPO-36,BeAPO-37, BeAPO-40, BeAPO-41, CAPO-5, CAPO-11, CAPO-31, CAPO-36,CAPO-37, CAPO-40, CAPO-41, GaAPO- 5, GaAPO-11, GaAPO-31, GaAPO-36,GaAPO-37, GaAPO-40, GaAPO-41, GeAPO-5, GeAPO-11, GeAPO-31, GeAPO-36,GeAPO-37, GeAPO-40, GeAPO-41, LiAPO-5, LiAPO-11, LiAPO-31, LiAPO-36,LiAPO-37, LiAPO-40, LiAPO-41, and the mixed-element APOs which may bedesignated MAPO-5, MAPO-11, MAPO-31, MAPO-36, MAPO-37, MAPO-40 andMAPO-41, and mixtures thereof.

The above characterization of the NZMSs which may be employed in theinstant invention relates to an adsorption characterization that iscarried out on a NZMS which has been subjected to a post synthesistreatment, e.g., calcination, hydrothermal treatment or chemicaltreatment, to remove a substantial portion of the template "R" which ispresent as a result of synthesis. Although a particular NZMS ischaracterized herein by reference to its adsorption of isobutane asbeing to the adsorption characteristics of the NZMS in its calcinedform, the instant invention necessarily includes the use of a noncalcined or modified NZMSs which may be characterized by such adsorptionin its calcined form, since upon use of such a non calcined NZMS in theinstant process at effective isomerization process conditions the NZMSmay be calcined or hydrothermally treated in situ so as to have thecharacteristic adsorption of isobutane. Thus, the NZMS may be renderedin situ to a form characterized by the aforementioned adsorptioncharacteristics. For example, an as synthesized MgAPO-11 or MgAPSO-11may not be characterized by the aforementioned adsorption of isobutanedue to the presence of template "R" which is present as a result ofsynthesis, although the calcined form of MgAPO-11 and MgAPSO-11 will becharacterized by the aforementioned adsorption of isobutane. Thus,reference to a NZMS having a particular adsorption characteristic in itscalcined or anhydrous form is not intended to exclude the use of theNZMS in its as-synthesized form which upon in situ calcination,hydrothermal treatment and/or other treatment, e.g., ion exchange withsuitable atoms, would have such adsorption characteristics.

Prior to contacting the gaseous stream and ammonia with the microporousnon zeolitic molecular sieve composition, the composition undergoesdealuminization by extraction with an acid, preferably a mineral acidsuch as nitric acid. The dealuminization proceeds readily at ambient orelevated temperatures and occurs with minimal losses in crystallinity,to form high silica forms of molecular sieve compositions withsilica:almumina ratios of at least 6.5:1, with ratios of 100:1 or evenhigher being readily attainable. Acid treatment with an inorganic ororganic acid is not required for certain non zeolitic molecular seivecompositions which do not contain Si (z is 0 in formula I above), forexample, the aluminophosphate molecular sieves.

The molecular sieve composition is conveniently used in the ammonium orhydrogen form for the dealuminization process although other cationicforms may also be employed, for example, the sodium form. If these otherforms are used, sufficient acid should be employed to allow for thereplacement by protons of the original cations in the molecular sievecomposition. The amount of molecular sieve composition in the molecularsieve composition/acid mixture should generally be from about 5 to about60 percent by weight.

The acid may be a mineral acid, i.e., an inorganic acid or an organicacid. Typical inorganic acids which can be employed include mineralacids such as hydrochloric, sulfuric, nitric and phosphoric acids,peroxydisulfonic acid, dithionic acid, sulfamic acid, peroxymonosulfuricacid, amidodisulfonic acid, nitrosulfonic acid, chlorosulfuric acid,pyrosulfuric acid, and nitrous acid. Representative organic acids whichmay be used include formic acid, trichloroacetic acid, andtrifluoroacetic acid.

The concentration of added acid should be such as not to lower the pH ofthe molecular sieve composition/acid mixture to an undesirably low levelwhich could affect the crystallinity of the molecular sieve compositionundergoing treatment. The acidity which the molecular sieve compositioncan tolerate will depend, at least in part, upon the silica/aluminaratio of the starting material. Generally, it has been found that themolecular sieve composition can withstand concentrated acid withoutundue loss in crystallinity but, as a general quide, the acid will befrom 0.1N to 4.0N, usually 1N to 2N. These values hold good regardlessof the silica:alumina ratio of the molecular sieve composition startingmaterial. Stronger acids tend to effect a relatively greater degree ofaluminum removal than weaker acids.

The dealuminization reaction proceeds readily at ambient temperatures,but elevated temperatures may be employed, e.g., up to about 100° C. Theduration of the extraction will affect the silica:alumina ratio of theproduct since extraction is time dependent. However, because themolecular sieve composition becomes progressively more resistant to lossof crystallinity as the silica:alumina ratio increases, i.e., it becomesprogressively more stable as the aluminum is removed, highertemperatures and more concentrated acids may be used, if desired,towards the end of the treatment than at the beginning without theattendant risk of losing crystallinity.

After the extraction treatment, the product may be water washed free ofimpurities, preferably with distilled water, until the effluent washwater has a pH within the approximate range of from about 5 to about 8.

The crystalline dealuminized products obtained by this acid extractionmethod have substantially the same crystallographic structure as that ofthe starting molecular sieve composition but with increasedsilica:alumina ratios as appropriate. The silica:alumina ratio willgenerally be in the range of from about 6.5:1 to about 500:1, moreusually from about 10:1 to about 250:1, e.g., 100:1 or more. Water ofhydration may also be present in varying amounts.

If desired, the molecular sieve composition may be hydrothermallytreated or steamed prior to acid extraction so as to increase theframework silica:alumina ratio as appropriate and render the molecularsieve composition more stable to the acid. In general, hydrothermaltreatment can be applied at a temperature of from about 500° C. to about850° C. or greater depending on the particular starting molecular sievecomposition. The steaming may also serve to increase the ease with whichthe aluminum is removed and to promote the retention of crystallinityduring the extraction procedure.

The molecular sieve composition is ion exchanged by contacting (with orwithout the presence of an inorganic oxide matrix component) saidmolecular sieve catalyst composition with a solution of at least onehydrogen forming cation, such as NH₄ ⁺, and H⁺ and quaternary ammonium,either after the acid extraction or simultaneously with the acidextraction described hereinabove. After acid treatment with an inorganicor organic acid and hydrogen forming cation exchange, the molecularsieve composition is metal cation exchanged. Suitable metal cationsinclude the cations of Group IIA, Group IIIA, Groups IIIB to VIIB, e.g.,nickel, cobalt, iron, manganese, copper, platinum, palladium, rhodiumand the like including mixtures thereof, and rare earth cations selectedfrom cerium, lanthanum, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, lutetium and mixtures thereof. Of course, the metal cationpresent as a result of ion exchange should have no substantial adverseeffect on the desired catalytic reduction of nitrogen oxides. As aresult of the ion exchange, the molecular sieve composition contains atleast one cation, e.g., hygrogen-forming cation and/or a metal cation,which is different form the cations initially associated with themolecular sieve composition as a result of its synthesis. The metalcation present as a result of ion exchange is preferably present inaneffective amount between about 0.1 weight percent and about 20 weightpercent, based on the weight of the starting molecular sieve compositionand is typically present in an effective amount between about 0.5 weightpercent and about 10 weight percent.

The metal cation exchange step is not required for certain non zeoliticmolecular sieve compositions which already contain a metal cation intheir as synthesized form, for example, MeAPO, MeAPSO, ELAPSO and thelike. However, non-zeolitic molecular seive compositions which contain ametal in their as-synthesized form may be further metal cation exchangedto provide a combination of different metals which may exhibit enhancedcatalytic properties.

The ion exchange is generally carried out by preparing a slurry of themolecular sieve composition by adding about 5 to 15 volumes of water pervolume of molecular sieve composition after which a solution of aselected cation is added. The ion exchange is generally carried out atroom temperature and the resulting solution is then heated to aboveabout 50° C. and stirred at this temperature for about 0.5 to 3 hours.This mixture is then filtered and water washed to remove excess anionpresent as a result of the solution of the cation salt.

For molecular sieve compositions in general, the desired metal can beincorporated into the molecular sieve structure by conventional porefilling techniques. As used herein, the term "metal cation exchanged"includes not only ion exchange but also pore filling and othertechniques which may be used to incorporate a cation into the molecularsieve structure.

Copending and commonly assigned U.S. patent application Ser. No.178,201), filed on an even date herewith and incorporated herein byreference, relates to a hydrocracking process for the production ofgasoline products utilizing catalysts which incorporate novel catalystbases prepared by sequentially hydrothermally treating followed by lowpH ammonium ion exchanging of a sodium Y-type zeolite. Such novelcatalyst bases are highly desirable for use as molecular sievecompositions herein

The molecular sieve compositions are typically employed with at leastone inorganic oxide matrix component, such inorganic oxide matrixcomponents typically employed heretofore in formulating molecular sievecatalyst compositions, including: amorphous catalytic inorganic oxidessuch as catalytically active silica/aluminas, clays, silicas, aluminas,silica-aluminas, silica-zirconias, silica-magnesias, silica thorias,silica-berylias, silica-alumina-thorias, silica-alumina-zirconias,alumina borias, alumina-titanias and the like and mixtures thereof. Thematrix may be in the form of a sol, hydrogel or gel and is typically analumina, silica or silica-alumina component such as a conventionalsilica-alumina catalyst, several types and compositions of which arecommercially available. The matrix may itself provide a catalyticeffect, such as that observed for catalytically active silica/aluminas,or it may be essentially inert. The matrix may act as a "binder" in someinstances although in some instances the final molecular sieve catalystcomposition may be spray dried or formed without the need of a binder.

These matrix materials may be prepared as a cogel of silica and aluminaor as alumina precipitated on the preformed and preaged hydrogel. Silicamay be present as a major matrix component in the solids present in thematrix, e.g., present in an amount between about 5 and about 40 weightpercent and preferably between about 10 and about 30 weight percent. Thesilica may also be employed in the form of a cogel comprising about 75weight percent silica and about 25 weight percent alumina or comprisingabout 87 weight percent silica and about 13 weight percent alumina. Theinorganic oxide matrix component will typically be present in the finalmolecular sieve catalyst composition in an amount between about 0 and 99weight percent, preferably between about 5 and about 90 weight percent,based on the total molecular sieve catalyst composition. It is alsowithin the scope of the instant invention to employ other materials withthe molecular sieve compositions in the final catalysts, includingclays, carbon monoxide oxidation promoters, etc.

Representative of matrix systems employable herein are disclosed inBritish patent specification No. 1,315,553, published May 2, 1973 andU.S. Pat. Nos. 3,446,727 and 4,086,187.

As above mentioned, the molecular sieve compositions used in the presentinvention may be employed with a matrix component and this may be asilica or alumina component. The alumina component may comprise discreteparticles of various aluminas, e.g., pseudoboehmite. The aluminacomponent may be in the form of discrete particles having a totalsurface area, as measured by the method of Brunauer, Emmett and Teller(BET), greater than about 20 square meters per gram (M² /g), preferablygreater than 145 M² /g, for example, from about 145 to about 300 M² /g.The pore volume of the alumina component will typically be greater than0.35 cc/g. The average particle size of the alumina particles isgenerally less than 10 microns and preferable less than 3 microns. Thealumina may be employed alone as the matrix or composited with the othermatrix components.

The alumina component may be any alumina and has preferably beenpreformed and placed in a physical form such that its surface area andpore structure are stabilized so that when the alumina is added to animpure, inorganic gel containing considerable amount of residual solublesalts, the salts will not alter the surface and pore characteristicsmeasurably nor will they promote chemical attack on the preformed porousalumina which could undergo change. For example, the alumina istypically an alumina which has been formed by suitable chemicalreaction, the slurry aged, filtered, dried, washed free of residual saltand then heated to reduce its volatile content to less than about 15weight percent. The alumina component may be present in the finalmolecular sieve catalyst composition in an amount ranging between about5 and about 95 weight percent, preferably between about 10 and about 30weight percent based on the total molecular sieve catalyst composition.Further, an alumina hydrosol or hydrogel or hydrous alumina slurry maybe used in the catalyst preparation.

Mixtures of the molecular sieve compositions and one or more inorganicoxide matrix components may be formed into a final form for themolecular sieve catalyst composition by standard catalyst formingtechniques including spray drying, pelleting, extrusion and othersuitable conventional means. The use of spray drying procedures is thepreferred means by which catalysts are prepared and such procedures arewell known in the art. The shape and size of the final molecular sievecatalyst composition can be chosen depending upon the applicationsintended. Various sizes of spherical, pellet and honeycomb monolithshaped structures can be used. The honeycomb type structure has theadvantage that it provides a system that has little pressure loss, evenwhen the flow velocity, i.e. the space velocity of the gaseous streamand ammonia is high. Honeycomb structures include those havingguadrangular, triangular and circular sectional shapes. It is alsopossible to use those having a sinusoidal wave, spider's web or spiralshape.

Catalysts containing the molecular sieve compositions may be prepared byany conventional method. One method of preparing such catalystsemploying silica alumina and porous alumina is to react sodium silicatewith a solution of aluminum sulfate to form a silica/alumina hydrogelslurry which is then aged to give the desired pore properties, filteredto remove a considerable amount of the extraneous and undesired sodiumand sulfate ions and then reslurried in water. The alumina may beprepared by reacting solutions of sodium aluminate and aluminum sulfateunder suitable conditions, aging the slurry to give the desired poreproperties of the alumina, filtering, drying, reslurry in water toremove sodium and sulfate ions and drying to reduce volatile mattercontent to less than 15 weight percent. The alumina may then be slurriedin water and blended in proper amounts, with a slurry of impure silicaalumina hydrogel. The molecular sieve composition may then be added tothis blend. A sufficient amount of each component is utilized to givethe desired final composition. The resulting mixture is then filtered toremove a portion of the remaining extraneous soluble salts therefrom.The filtered mixture is then dried to produce dried solids. The driedsolids are subsequently reslurried in water and washed substantiallyfree of the undesired soluble salts. The molecular sieve catalystcomposition is then dried to a residual water content of less than about15 weight percent. The molecular sieve catalyst composition is typicallyemployed after a calcination or activation.

Calcination or activation is typically conducted after preparation ofthe molecular sieve catalyst composition. It is understood thatcalcination or activation treatment may be carried out one or more timesin any order and that such variations are within the scope of thisinvention. For example, one calcination or activation may be carried outprior to combining the molecular sieve composition with an inorganicoxide matrix component and a second calcination or activation may becarried out after combining the molecular sieve composition with aninorganic oxide matrix component.

The conditions at which the catalytic reduction of nitrogen oxidesoccurs can vary widely. The reduction reaction temperature can beconducted over a wide range, but, in general, in the range from about200° C. to about 650° C., which is the expected temperature range forthe usual flue gas. Although pressure is not a critical factor in themethod of this invention, the preferred pressure of the gaseous streamwill be from about atmospheric to about 10 pounds per square inch gauge,which is the expected pressure range for the usual flue gas. Spacevelocities of from about 1,000 hr⁻¹ up to about 1 million hr⁻¹,preferably from about 5,000 hr⁻¹ to about 500,000 hr⁻¹, can be used inthe catalytc reduction of nitrogen oxides according to this invention.The non zeolitic molecular sieve composition should be sufficientlystable to maintain its crystalline structure and catalytic activityafter exposure to the gaseous stream.

In a preferred embodiment of this invention, a gaseous streamcomposition containing nitric oxide and sulfur dioxide such as a fluegas obtained from power plants, gas turbines or the like or tail gasstreams from nitric acid manufacture is mixed with ammonia and contactedwith the molecular sieve catalyst composition. Depending upon the nitricoxide concentration, the concentration of ammonia is preferably fromabout 0.9 to about 1.3 moles per mole of nitrogen oxide (NO_(x)) in thegaseous stream. The reaction temperature which can be utilized in themethod wherein the production of nitrogen is maximized and theproduction of nitrogen oxide is minimized is preferably between about100° C. and about 450° C. The molecular sieve catalyst composition isemployed at space velocities preferably between about 2500 hr⁻¹ and25,000 hr⁻¹. In addition, increased conversion rates can be attained byutilizing a plurality of catalyst beds which the gaseous stream contactsserially.

EXAMPLE 1

LZ-210, a crystalline aluminosilicate zeolite molecular sieve having aSiO₂ /Al₂ O₃ molar ratio of 12 and obtained from Union CarbideCorporation, Danbury, Connecticut, was copper exchanged three timesusing one part by weight copper sulfate to one part by weight LZ-210 ata temperature of 85° C. for a period of one hour for each exchange. Theresulting copper exchanged LZ-210 was then dried at a temperature of100° C. After drying, the copper exchanged LZ-210 product was combinedwith 20 weight percent Ludox AS-40 gelled with ammonium acetate andextruded as a 1/16-inch extrudate. The extrudate was activated in a dryair purged oven over a period of 2.5 hours to a temperature of 500° C.and thereafter maintained at that temperature for an additional 1.5hours. The extrudate product contained 5.2 weight percent of copper.

This product is referred to hereinafter as Catalyst A.

EXAMPLE 2

LZ-210, a crystalline aluminosilicate zeolite molecular sieve having aSiO₂ /Al₂ O₃ molar ratio of 12 and obtained from Union CarbideCorporation, Danbury, Connecticut, was potassium exchanged 3 times usingone part by weight potassium chloride to one part by weight LZ-210 at atemperature of 85° C. for a period of one hour for each exchange. Thepotassium exchanged LZ-210 was then copper exchanged two times using onepart by weight copper sulfate to one part by weight potassium exchangedLZ-210 at a temperature of 85° C. for a period of one hour for eachexchange. The resulting copper-potassium exchanged LZ-210 was then driedat a temperature of 100° C. After drying, the copper potassium exchangedLZ-210 product was combined with 20 weight percent Ludox AS 40 gelledwith ammonium acetate and extruded as a 1/16-inch extrudate. Theextrudate was activated in a dry air purged oven over a period of 2.5hours to a temperature of 500° C. and thereafter maintained at thattemperature for an additional 1.5 hours. The extrudate product contained5.0 weight percent of copper and 2.2 weight percent of potassium.

This product is referred to hereinafter as Catalyst B.

EXAMPLE 3

LZ-210, a crystalline aluminosilicate zeolite molecular sieve having aSiO₂ /Al₂ O₃ molar ratio of 12 and obtained from Union CarbideCorporation, Danbury, Connecticut, was copper exchanged three timesusing on part by weight copper sulfate to one part by weight LZ-210 at atemperature of 85° C. for a period of one hour for each exchange. Thecopper exchanged LZ-210 was then potassium exchanged 3 times using onepart by weight potassium chloride to one part by weight copper exchangedLZ-210 at a temperature of 85° C. for a period of one hour for eachexchange. The resulting potassium copper exchanged LZ-210 was then driedat a temperature of 100° C. After drying, the potassium copper exchangedLZ-210 product was combined with 20 weight percent peptized alumina andextruded as a 1/16-inch extrudate. The extrudate was activated in a dryair purged oven over a period of 2.5 hours to a temperature of 500° C.and thereafter maintained at that temperature for an additional 1 5hours. The extrudate product contained 5.2 weight percent of copper and2.3 weight percent of potassium.

This product is referred to hereinafter as Catalyst C.

EXAMPLE 4

Nitric acid extracted, ammonium exchanged mordenite, a one dimensionalcrystalline aluminosilicate zeolite molecular sieve having a SiO₂ /Al₂O₃ molar ratio of 18 and obtained from Union Carbide Corporation,Danbury, Connecticut, was copper exchanged two times using 0.33 moles ofcopper to one mole of Al₂ O₃ at a temperature of 85° C. for a period ofone hour for each exchange. The resulting copper exchanged mordenite wasthen dried at a temperature of 100° C. After drying, the copperexchanged mordenite product was combined with 20 weight percent LudoxAS-40 gelled with ammonium acetate and extruded as a 1/16-inchextrudate. The extrudate was activated in a dry air purged oven over aperiod of 2.5 hours to a temperature of 500° C. and thereaftermaintained at that temperature for an additional 1.5 hours. Theextrudate product contained 1.4 weight percent of copper.

This product is referred to hereinafter as Catalyst D.

EXAMPLE 5

LZ-210, a crystalline aluminosilicate zeolite molecular sieve having aSiO₂ /Al₂ O₃ molar ratio of 9 and obtained from Union CarbideCorporation, Danbury, Connecticut, was copper exchanged three timesusing one part by weight copper sulfate to three parts by weight LZ-210at a temperature of 85° C. for a period of one hour for each exchange.The resulting copper exchanged LZ-210 was then dried at a temperature of100° C. After drying, the copper exchanged LZ-210 product was combinedwith 20 weight percent Ludox AS-40 gelled with ammonium acetate andextruded as a 1/16-inch extrudate. The extrudate was activated in a dryair purged oven over a period of 2.5 hours to a temperature of 500° C.and thereafter maintained at that temperature for an additional 1.5hours. The extrudate product contained 4.3 weight percent of copper.

This product is referred to hereinafter as Catalyst E.

EXAMPLE 6

Silicalite, a crystalline silica molecular sieve having a SiO₂ /Al₂ O₃molar ratio of about 25 and commercially available, was combined with 20weight percent Ludox AS-40 gelled with ammonium acetate, pore filledwith about 3.5 weight percent of copper, and then extruded as a1/16-inch extrudate. The extrudate was activated in a dry air purgedoven over a period of 2.5 hours to a temperature of 500° C. andthereafter maintained at that temperature for an additional 1.5 hours.The extrudate product contained 3.7 weight percent of copper.

This product is referred to hereinafter as Catalyst F.

EXAMPLE 7

LZ-105, a crystalline aluminosilicate zeolite molecular sieve having aSiO₂ /Al₂ O₃ molar ratio of 40 and obtained from Union CarbideCorporation, Danbury, Connecticut, was calcined at a temperature ofabout 600° C. for a period of 2.0 hours.

After calcination, the LZ-105 was acid extracted with a 70 percentnitric acid aqueous solution at a temperature of 93° C. for a period ofone hour, and then ammonium exchanged 3 times with a 15 weight percentammonium nitrate aqueous solution using 1.5 parts by weight ammoniumnitrate to 1.0 part by weight LZ-105 at a temperature of 93° C. for aperiod of one hour for each exchange.

After acid extraction and ammonium exchange, LZ-105 was copper exchangedthree times using one part by weight copper sulfate to three parts byweight LZ-105 at a temperature of 85° C. for a period of 1.0 hour foreach exchange.

The resulting ammonium-copper exchanged LZ-105 was then combined with 20weight percent peptized alumina and extruded as a 1/16-inch extrudate.The extrudate was activated in a dry air purged oven over a period of2.5 hours to a temperature of 500° C. and thereafter held at thattemperature for an additional 1.5 hours. The extrudate product contained3.0 weight percent of copper.

This product is referred to hereinafter as Catalyst 1.

EXAMPLE 8

Sodium Y zeolite (Y-52), a crystalline aluminosilicate zeolite molecularsieve having a SiO₂ /Al₂ O₃ molar ratio of about 5.0 and commerciallyavailable, was ammonium exchanged 3 times with a 15 weight percentammonium nitrate aqueous solution using 1.0 part by weight ammoniumnitrate to 1.0 part by weight Y-52 at a temperature of 85° C. for aperiod of one hour for each exchange. The ammonium exchanged Y-52 waswashed between exchanges with 2 gallons of water to one pound of Y-52.The resulting ammonium exchanged Y-52 was then dried at a temperature of100° C.

After drying, the resulting ammonium exchanged Y-52 was hydrothermallytreated (100 percent steam) at a temperature of about 700° C. for aperiod of 1.0 hour. The hydrothermally treated ammonium exchanged Y-52was designated as Y-72.

After hydrothermal treatment, the resulting Y-72 was again ammoniumexchanged three times with a 15 weight percent ammonium nitrate aqueoussolution using 1.5 parts by weight ammonium nitrate to 1.0 part byweight Y-72 at a temperature of 85° C. for a period of one hour for eachexchange. In addition, 70 percent nitric acid aqueous solution was addedto each exchange to lower the pH of each exchange to less than 4.0. ThepH was adjusted with 70 percent nitric acid aqueous solution at thebeginning of each exchange without further addition thereof.

After the final ammonium exchange at low pH, the ammonium exchanged Y-72was copper exchanged three times using one part by weight copper sulfateto one part by weight Y-72 at a temperature of 85° C. for a period of1.0 hour for each exchange.

The resulting ammonium-copper exchanged Y-72 having a SiO₂ /Al₂ O₃ molarratio of 12 was then combined with 20 weight percent peptized aluminaand extruded as a 1/16-inch extrudate. The extrudte was activated in adry air purged oven over a period of 2.5 hours to a temperature of 500°C. and thereafter held at that temperature for an additional 1.5 hours.The extrudate product contained 3.0 weight percent of copper.

This product is referred to hereinafter as Catalyst 2.

EXAMPLES 9-24

The catalyst compositions prepared in Examples 1-8 above were evaluatedfor reductive removal of nitrogen oxide (NO) from a simulated flue gasusing ammonia as a reducing agent. The simulated flue gas contained NOand SO₂ in the amounts (parts per million) specified in Table A below inaddition to oxygen, carbon dioxide, water vapor and nitrogen in varyingproportions. The weight percent ratio of oxygen to ammonia for each ofthe examples in Table A was 5.0. The simulated flue gas and ammonia werepassed through a tubular reactor (22 millimeter internal diameter)containing a catalyst packed bed at a flow rate of 50 h⁻¹ (50×10⁻³ cubicmeters/hour). The catalyst packed bed contained 5.0 grams of thecatalyst (pellet form) specified for each example in Table A and thedensity of the catalyst packed bed was 500 kilograms/cubic meter. Thereactor temperature for each example in Table A was 350° C. and thespace velocity (volume flow/total volume) was 20,000 h⁻¹. Theperformance of the catalyst used in each example in Table A wasevaluated in terms of percent NO reduction (percent NO removal). Theresults are given in Table A.

                                      TABLE A                                     __________________________________________________________________________         Catalyst                                                                             NO into SO.sub.2 into                                                                         NH.sub.3 /NO                                                                         NH.sub.3 Oxidation                                                                     NO Removal                        Example                                                                            Identification                                                                       Reactor (ppm)                                                                         Reactor (ppm)                                                                         (Molar Ratio)                                                                        (Weight Percent)                                                                       (Weight Percent)                  __________________________________________________________________________    9    A      10,000  0       1.14   37       87.5                              10   A      10,000  7,000   1.15   --       75.0                              11   B      10,000  0       1.19   95       91.6                              12   B      10,000  7,000   1.14   --       76.0                              13   C      10,000  0       1.20   94       89.2                              14   C      10,000  7,000   1.15   --       86.5                              15   D      10,000  0       1.13   93       93.2                              16   D      10,000  7,000   1.13   --       76.8                              17   E      10,000  0       1.17   98       83.7                              18   E      10,000  7,000   1.17   --       74.2                              19   F      10,000  0       1.17   98       81.0                              20   F      10,000  7,000   1.17   --       74.2                              21   1      8,220   0       1.15   75       95.5                              22   1      7,650   7,000   1.24   --       96.1                              23   2      8,300   0       1.15   70       94.0                              24   2      7,620   7,000   1.15   --       98.4                              __________________________________________________________________________

We claim:
 1. A method for catalytically reducing one or more nitrogenoxides from a gaseous stream containing one or more nitrogen oxides andone or more sulfur oxides which comprises contacting said gaseous streamand ammonia with a microporous non-zeolitic molecular sieve compositionat effective reduction conditions, wherein said microporous non-zeoliticmolecular sieve composition is hydrogen-forming cation exchanged priorto said contacting in said method.
 2. The method of claim 1 wherein saidmicroporous non-zeolitic molecular sieve composition is dealuminized byacid treatment with an acid selected from nitric acid, sulfuric acid,hydrocholoric acid, phosphorus acid, formic acid and trichloroaceticacid.
 3. The method of claim 2 wherein said microporous non-zeoliticmolecular sieve composition is acid treated with nitric acid.
 4. Themethod of claim 1 wherein said microporous non-zeolitic molecular sievecomposition is hydrogen-forming cation exchanged with a hydrogen-formingcation selected from NH₄ ⁺, H⁺ or quaternary ammonium.
 5. The method ofclaim 4 wherein said microporous non-zeolitic molecular sievecomposition is hydrogen-forming cation exchanged with NH₄ ⁺.
 6. Themethod of claim 1 wherein said microporous non-zeolitic molecular sievecomposition is metal cation exchanged with a metal selected from copper,cobalt, vanadium, chronium, tungsten, nickel, platinum, palladium,manganese, molybdenum, rhodium, magnesium, aluminum and iron.
 7. Themethod of claim 6 wherein said microporous non-zeolitic molecular sievecomposition is metal cation exchanged with copper.
 8. The method ofclaim 2 wherein said microporous non-zeolitic molecular sievecomposition is simultaneously acid treated with an inorganic or organicacid and hydrogen-forming cation exchanged.
 9. The method of claim 2wherein said microporous non-zeolitic molecular sieve composition ishydrogen-forming cation exchanged prior to being acid treated with aninorganic or organic acid.
 10. The method of claim 1 wherein saidmicroporous non-zeolitic molecular sieve composition is hydrothermallytreated with steam prior to being acid treated with an inorganic ororganic acid.
 11. The method of claim 10 wherein said microporousnon-zeolitic molecular sieve composition is hydrogen-forming cationexchanged and hydrothermally treated with steam prior to being acidtreated with an inorganic or organic acid.
 12. The method of claim 1wherein said microporous non-zeolitic molecular sieve composition isselected from SAPOs, ELAPSOs, AlPO₄ s, MeAPOs, FeAPOs, TAPOs, ELAPOs andMeAFSOs.
 13. The method of claim 1 wherein said microporous non-zeoliticmolecular sieve composition is a SAPO molecular sieve.
 14. The method ofclaim 1 wherein said microporous non-zeolitic molecular sievecomposition is an ELAPSO molecular sieve.
 15. The method of claim 1wherein said microporous non-zeolitic molecular sieve composition is aMeAPSO molecular sieve.
 16. The method of claim 1 wherein saidmicroporous non-zeolitic molecular sieve composition is an ELAPSOmolecular sieve.
 17. The method of claim 1 wherein said microporousnon-zeolitic molecular sieve composition is a MeAPO molecular sieve. 18.The method of claim 1 wherein said microporous non-zeolitic molecularsieve composition is an AlPO₄ molecular sieve.
 19. The method of claim 1wherein said microporous non-zeolitic molecular sieve composition is aTAPO molecular sieve.
 20. The method of claim 1 wherein said microporousnon-zeolitic molecular sieve composition is supported in an inorganicoxide matrix.
 21. The method of claim 20 wherein the inorganic oxidematrix is predominantly silica.
 22. The method of claim 1 wherein thegaseous stream contains at least nitrogen dioxide and sulfur dioxide.23. The method of claim 1 in which ammonia is present in an amountsufficient to result in a molar ratio of said ammonia to said nitrogenoxides of from about 0.50:1 to about 1.50:1.
 24. The method of claim 1wherein said gaseous stream and ammonia are contacted with saidmicroporous non-zeolitic molecular sieve composition at a temperature offrom about 100° C. to about 650° C.
 25. The method of claim 1 whereinsaid microporous non-zeolitic molecular sieve composition at a pressureof from about atmosphere to about 10 psig.
 26. The method of claim 1wherein said gaseous stream and ammonia are passed through saidmicroporous non-zeolitic molecular sieve composition at a space velocityof from about 1000 to about 150,000 hr⁻¹.